Cette thèse est divisée en trois parties. La première traite la synthèse de la polyaniline (PANI), un polymère conducteur de trou, utilisé dans plusieurs applications. En variant les quantités du monomère et de l’oxydant tout en fixant leur rapport molaire à 1:1,25, et en ajoutant de l’oxyde de magnésium, des aiguilles et des nouvelles structures semblables aux échinides sont formées. Le mécanisme de formation des structures unidimensionnelles est expliqué à l’aide de la théorie des multicouches. La deuxième partie est consacrée à la fabrication des monocouches photovoltaïques à faible coût en se basant sur le principe de fonctionnement des cellules à pigment photosensible (en anglais DSSC, Dye-Sensitized Solar Cell). En 1991, Grätzel a réintroduit l’effet photo-électrochimique en développant la première DSSC, une des cellules solaire troisième génération, formée d’un film de TiO2 (photo-anode) pigmenté à l’aide d’un colorant et d’un électrolyte qui sert à régénérer le pigment oxydé. Malgré leur faible coût, les DSSCs font face à de nombreux problèmes tels que le coût élevé du pigment, la fuite de l’électrolyte, la sublimation du couple I-/I3- à travers I2, etc. Afin de résoudre ces problèmes, des monocouches photovoltaïques ont été développées. Des composites formés de PANI et TiO2 sont la base de ces dispositifs nouvelle génération. La polymérisation in-situ de l’aniline en présence des nanoparticules de TiO2 conduit à une forte interaction entre la PANI et les particules de TiO2 où une structure « core (TiO2)/shell (PANI) » existe dans le composite. Dans le dispositif photovoltaïque basé sur le composite PANI-TiO2, PANI est considérée comme pigment à la photo-anode et comme poly-électrolyte plus profondément dans le composite. En plus, des textiles fabriqués utilisant ces composites photo-génèrent une tension de 0,6 V et un courant de 1 A/m2 lorsque l’éthanol est injecté dans le dispositif. Une nouvelle architecture a été développée qui sert à améliorer la performance de la cellule et en même temps stocker l’énergie pour des utilisations ultérieures. La dernière partie est consacrée à la fabrication des DSSCs basées sur les pigments naturels. L’anthocyane, un pigment naturel halochromique responsable de la couleur rouge dans les plantes, a été extrait du chou rouge et utilisé pour pigmenter les films de TiO2. Cette propriété se traduit par la fabrication des DSSCs de différentes couleurs et comportement photovoltaïque. Avec un pH égal à 0, une Vco et une Jcc de 520 mV et 185 μA/cm2 sont respectivement obtenues prouvant la possibilité d’utiliser le chou rouge comme source de pigment à très faible coût des DSSCs. / This thesis is divided in three parts. The first one deals with the synthesis of polyaniline (PANI), a hole conducting polymer, used in many applications. By varying the quantities of the monomer and the oxidant while fixing the molar ratio at 1:1.25, and by adding magnesium oxide, novel echinoid-like and PANI needles were formed. The formation mechanism of the 1D structures is explained using the multi-layer theory. The second section is devoted for the fabrication of low cost single-layered photovoltaic devices based on the working principle of dye-sensitized solar cells (DSSCs). In 1991, Grätzel reintroduced the photo-electrochemical effect by developing the first DSSC, one of the third generation solar cells, formed of a TiO2 film (photoanode) sensitized using a dye and an electrolyte regenerating the excited dye. Despite their low cost, DSSCs face many problems such as the high cost of the dye, leaking of the electrolyte, sublimation of the I-/I3- through I2, etc. To solve these problems a single layer photovoltaic device has been developed. Composites formed of PANI, and TiO2 are the basis of the new generation photovoltaics. The in-situ polymerization of aniline inside a titania solution results in a strong interaction between PANI and TiO2 particles where a core (TiO2)/shell (PANI) structure exists inside the composite. In the single-layered photovoltaic device based on PANI-TiO2 composite, PANI is considered as sensitizer at the photoanode and as polyelectrolyte deeper inside the composite layer. In addition, textiles fabricated using such composites generated a voltage of 0.6 V and a current of 1 A/m2 when ethanol is injected in the solar cell. A new architecture has been developed to enhance the performance of the device and at the same time to store the converted energy for later use. The final part is devoted to the fabrication of DSSCs based on natural dyes. Anthocyanin; a halochromic natural dye responsible for the red color in plants, extracted from red cabbage was used to sensitize TiO2 films. This property results in the fabrication of DSSCs with different colors and photovoltaic behavior. At a pH equal to 0, a Voc and Jsc of 520 mV and 185 μA/cm2 were respectively recorded proving the possibility of using red cabbages as a very low cost dye source for DSSCs.

Flavonoids are plant secondary metabolites, which belong to several groups varying in their chemical structure. Anthocyanins and tannins are important flavonoid components of wine that are responsible for its color, taste and other sensory properties. The concentration of anthocyanins in wine is affected by grape variety, processing technology, and climatic conditions. In this Thesis, we studied the changes in color and in related chemical composition, using three non-commercial samples of red wine: Svatovavřinecké (year 2010 and 2012), and home-made wine (prepared without addition of SO2). These changes in color were determined using standard colorimetric method (CIELab) and also a simplified two-parametric spectrophotometric method (tint/color density). The content of anthocyanins was followed using analytical RP-HPLC method. In paralel, simplified oenologic methods for estimation of phenolic compounds were used. Generally the wine samples changed color to darker tint. Chemically, this was caused by polymerisation reactions between anthocyanins and phenolic compounds. This led to the formation of stable pigments characterised by a higher absorption maximum at longetr wavelength, hence a darker tint. Key words: anthocyanins, color, red wine, phenolic compounds, malvidin-3-glucosid, polymeric reactions,...

Depuis les révolutions industrielles des années 1700 et 1800, et pendant l'industrialisation des siècles les suivant, une accumulation de composés polluants a eu lieu dans l'atmosphère, principalement due à la combustion de matières fossiles comme le charbon et le pétrole. Outre les polluants directement émis comme les oxydes de souffre et d'azote, des polluants secondaires comme l'ozone se sont accumulés. Aujourd'hui, l'ozone est le troisième gaz responsable du réchauffement climatique, mais est également dangereux pour la santé humaine et responsable de dommages sur la végétation. Depuis les années cinquante, les effets de l'ozone sur les plantes et les réponses de ces dernières ont été étudiés de façon ciblée. Aujourd'hui, avec l'apparition de techniques permettant l'étude globale du transcriptome ou du protéome, il est possible d'aborder le problème d'une façon non biaisée, permettant des études plus complètes du stress. Dans le cadre de ce travail, une étude protéomique des effets de l'ozone sur les processus foliaires du peuplier a été proposée. Cette technique, complétée par des approches biochimiques, physiologiques, et des observations morphologiques, a permis de confirmer certains résultats d'études ciblées, mais également d'émettre des nouvelles hypothèses sur les mécanismes d'action de l'ozone sur le métabolisme du peuplier. En parallèle, l'étude du stress a aussi permis d'éclaircir les changements du métabolisme lors de la croissance de feuilles en conditions de stress et en conditions normales. Dans les pages de ce document, les procédures, résultats et conclusions de ce travail seront présentés en détail / After the industrial revolution of the 1700s and 1800s, and the subsequent industrialization, many pollutants have accumulated in the atmosphere, mainly due to the use of coal and fossil fuels. Besides the primary pollutants such as nitrogen oxides and sulfur oxides, secondary oxides such as ozone started to accumulate. Nowadays, ozone is the third gas involved in global climate change, but is also a major health risk for humans, and induces considerable damage to vegetation. Starting in the 50s, ozone research was based on targeted studies. Nowadays, with the advent of global techniques such as transcriptomics and proteomics, new results can be produced in an unbiased way. In the thesis presented here, a proteomic study of the effects of ozone on poplar leaf processes was carried out. With the help of this technique, complemented with biochemical and physiological approaches and with morphological observations, it was possible to confirm previous results, but also to elaborate new hypotheses concerning the effects of ozone on poplar leaf metabolism. In parallel, studying the stress also allowed to clarify some of the changes that occur in metabolism during leaf development, under stress conditions and under control conditions. In this document, the procedures, results and conclusions obtained during this study are presented in detail

The aim of this work was to develop a solid knowledge on formulation effects controlling offset ink-paper coating adhesion and to identify key factors of the coating and printing process affecting it. Focus lay on comprehending the impact of pigment dispersant on ink-paper coating adhesion and ultimately on the print quality of offset prints. The work covers laboratory studies, a pilot coating trial designed to produce coated material with a span in surface chemistry and structure, and an industrial offset printing trial. The lab scale studies quantified ink-paper coating adhesion failure during ink setting with a developed laboratory procedure based on the Ink-Surface Interaction Tester (ISIT) and image analysis. Additional polyacrylate dispersant resulted in slower ink setting and reduced ink-paper coating adhesion, with a dependence on its state of salt neutralisation and cation exchange, mainly in the presence of moisture/liquid water. The industrial printing trial on pilot coated papers was designed to study how these laboratory findings affected full scale offset print quality. These trials confirmed the dispersant-sensitive effect on ink-paper coating adhesion, especially at high water feeds. Evaluation of prints from the printing trial resulted in two fundamentally different types of ink adhesion failure being identified. The first type being traditional ink refusal, and the second type being a novel mechanism referred to as ink-lift-off adhesion failure. Ink-lift-off adhesion failure occurs when ink is initially deposited on the paper but then lifted off in a subsequent print unit. In this work, ink adhesion failure by this ink-lift-off mechanism was observed to occur more often than failure due to ink refusal. Print quality evaluation of the industrial prints suggested that water induced mottle was caused by a combination of ink-surface adhesion failure, creating white spots on the print, together with variation in ink layer thickness due to emulsified ink. / <p>QC 20161019</p>

Verificou-se que microssomos de fígado apresentam uma atividade azo-redutásica completamente dependente de NADPH, usando DAB como substrato. Ao contrário de outros sistemas já descritos, a atividade azo-redutásica não pode ser identificada com a NADPH-citocromo c redutase, embora nossos resultados indiquem que esta enzima participa da reação. Não se pode excluir definitivamente a participação do citocromo b5 apesar de uma série de observações afastando essa possibilidade. Verificou-se que a atividade azo-redutásica pode ser induzida por tratamento com 3-MC, paralelamente à indução do citocromo P-450 tipo II. Isto sugere fortemente a participação desse citocromo na reação apesar desta não ser inibida por CO. O citocromo P-450 induzido por tratamento com 3-MC era funcionalmente ativo. A atividade azo-redutásica foi inibida especificamente pelo tratamento oral comoDAB, possibilitando a formulação de uma hipótese sobre a ação carcinogênica deste composto. Uma série de resultados mostra que a azo-redutase estudada é altamente específica podendo ser inibida por KCN e por mersalil. Face aos fatos expostos acima, as perspectivas do sistema parecem muito interessantes. A possibilidade do uso de novos métodos de fracionamento dos microssomos pode levar à resolução do sistema da azo-redutase. As semelhanças com a dessaturação de ácidos graxos, aliadas às indicações da existência de um novo tipo de citocromo P-450 que se combina com KCN, permitem descortinar maior amplitude para os limites do sistema da azo-redutase. Enfim, trata-se de uma reação de redução de um composto exógeno, com características até agora não relatadas, envolvendo processos biológicos de importância e cujo estudo terá prosseguimento. / Not available

Este trabalho envolve o estudo sobre os níveis de pigmentos fotossintéticos, carotenóides e clorofilas, presentes nas algas marinhas Tetraselmis gracilis e Gracilaria tenuistipitata, em condições de senescência celular e estresse antropogênico (poluição metálica). Em razão do papel fundamental dos carotenóides na organização de membranas tilacóides, o papel estrutural de carotenos e do extrato metanólico de T. gracilis em bicamadas lipídicas também foi avaliado. Para estes estudos foram realizados o cultivo, coleta e construção das curvas de crescimento das algas, obtenção dos cromatogramas típicos, identificação de alguns pigmentos fotossintéticos através de padrões, análise dos extratos brutos em diferentes fases de crescimento e respectiva quantificação. Foram realizados bioensaios de toxicidade dos metais Cd, Cu, Hg e Pb e foram estimados os parâmetros toxicológicos CE15 e CE50 (concentração efetiva para a redução de 15 e 50%, respectivamente, do crescimento algal). Os modelos de estresse agudo e crônico foram construídos para cada metal e a quantificação dos pigmentos fotossintéticos foi realizada. Lipossomos foram confeccionados com a incorporação de carotenos e do extrato metanólico de T. gracilis na bicamada e foram realizadas medidas de espalhamento de luz, de calorimetria, do diâmetro hidrodinâmico e de fosfolípides. A cinética de liberação e de permeação de NO foi estudada através de medidas de fluorescência e de quimiluminescência. Também foi realizada a extração e pré-isolamento dos carotenóides presentes em T. gracilis. Os mecanismos de defesa contra espécies reativas de oxigênio foram diferentes em razão das distintas variações observadas nos níveis de pigmentos para cada metal estudado e tipo de estresse. Também foi observado um aumento do nível de pigmentos em função do aumento do tempo de exposição correspondendo provavelmente a uma estratégia aclimatativa extremamente importante no papel de adaptação e sobrevivência de organismos fotossintéticos, o que torna este tipo de avaliação, principalmente dos níveis de carotenóides, uma ferramenta útil como parâmetro de avaliação de poluição ambiental, além do emprego da biomassa como ferramenta de biorremoção de metais. Em relação aos valores de CE50 observados, o valor encontrado para o Cu foi inferior ao padrão previsto na Resolução do CONAMA no 357. Portanto, efluentes contendo Cu em níveis permitidos poderão causar danos à biota marinha. Mais ainda, sugere-se que os limites recomendáveis para este metal deverão ser revistos e alterados para a preservação de ecossistemas aquáticos. A incorporação do extrato de T. gracilis ocasionou uma grande perturbação na estruturação da membrana, resultando na fluidificação da bicamada lipídica, independente da fase de crescimento. O &#946;-caroteno e o licopeno interferem na estruturação de bicamadas lipídicas diminuindo o diâmetro hidrodinâmico das vesículas unilamelares grandes, efeito ainda não descrito na literatura, reduzindo o valor da temperatura na qual se inicia a transição de fase, alargando a faixa onde ocorre a transição, reduzindo os valores capacidade calorífica e da entalpia e, conseqüentemente, modificando a cooperatividade da transição. Somente o &#946;-caroteno causou fluidificação do sistema lipídico e aumento da velocidade de permeação de NO através da membrana, sugerindo o provável papel do &#946;-caroteno na modulação de propriedades físicas da membrana. / This work involves the study of the levels of photosynthetic pigments, carotenoids and chlorophylls, contained in the marine algae Tetraselmis gracilis and Gracilaria tenuistipitata, under conditions of cellular senescence and anthropogenic stress (metallic pollution). Due to the fundamental organizational role of carotenoids in thylakoid membranes, its structural features in lipid bilayers were evaluated. Also in this last mentioned study, it was employed the methanolic extract of T. gracilis. In order to perform these studies, the algae were cultivated and the growth curves determined. Also, the typical chromatograms were obtained, and some photosynthetic pigments were identified trough commercial standards, which were then analyzed and quantified in crude extracts of different growth phases. The toxicity of the metals Cd, Cu, Hg and Pb were determined trough bioassays, which led to the toxicological parameters EC15 and EC50 estimation (the effective concentration that causes 15 and 50% of reduction of the algal growth, respectively). For each metal, the acute and chronic stress models were built, and the photosynthetic pigments contents\' quantified. Liposomes were constructed with the incorporation of carotenes and of the T. gracilis\' methanolic extract in the bilayer, which were then submitted to light scattering, calorimetric, hydrodynamic radius and phospholipid assays. Fluorescence and chemiluminescence measurements were used to study the NO kinetics of liberation and permeation. Also, it was accomplished the extraction and pre-isolation of carotenes contained in T. gracilis. For each type of metal and stress occasioned, different levels of pigments were observed, a consequence of the different mechanisms employed against reactive oxygen species. At higher exposure periods, higher pigments\' contents were quantified, which probably corresponds to an algae acclimatative strategy. The EC50 value found for Cu is higher than the standard one previously stated in the CONAMA\'s nº 357 resolution. This means that effluents containing Cu, in levels allowed by the law, may cause damage to the marine biota. Moreover, it\'s suggested a reevaluation of the standard limiting value for this metal, in order to preserve aquatic ecosystems. A higher fluidity of the lipid bilayer, occasioned by a large perturbation of the membrane\'s structure, was accomplished by incorporating the extract of T. gracilis. This was observed independently of the cells\' growth phase. &$946;-carotene and licopene interfere in the lipid bilayer structure, lowering the hydrodynamic diameter of large unilamellar vesicles, an effect not previously reported in literature. This reduces the temperature were the phase transition initiates, broadens the transition gap, lowers the calorific capacity and enthalpy values, consequently, modifying the transition cooperation. Only &#946;-carotene induces a higher fluidity of the lipid system and a faster NO permeation trough the membrane, which suggests that it may modify physical properties of the membrane.

Gracilaria caudata J. Agardh is one of the naturally occurring species in Brazil that produce good quality agar. In Rio do Fogo (RN), Brazil, a green variant was discovered in a G. caudata population of predominantly red (wild phenotype) tetrasporophytes. Epiphytes gametophytes on tetrasporophytes have been observed for both strains. Considering the wild and green variant strains in laboratory control conditions, this study: (i) assessed the impacts of epiphyte gametophytes on tetrasporophytes by evaluating the growth rates, the pigment content, and the photosynthetic potential of the tetrasporophytes; (ii) evaluated the amount of time required for the differentiation of cystocarps in free-living gametophytes and epiphyte gametophytes on tetrasporophytes; (iii) evaluated the number of epiphyte gametophytes produced by tetrasporophyte; and (iv) analyzed anatomical aspects of the intersection between the tetrasporophytes and the tetraspores that germinated on the tetrasporophytes. Samples were cultivated for 12 weeks on laboratory conditions. Control samples had epiphyte gametophytes growing on them, while treatment samples had their epiphyte gametophytes removed weekly. Physiological analyses compared control and treatment samples, while anatomical analysis used the control samples only. Considering the tetrasporophyte growth rates before fertility (2nd week), wild strain showed higher values than green variant; however, after 12 weeks, no differences were found between strains or between samples without epiphyte gametophytes. The wild strain produced tetraspores more frequently than the green variant and showed deficiency in phycoerythrin and allophycocyanin. Green variant treatment samples had higher content of allophycocyanin, phycocyanin and phycoerythrin than the control samples. Chlorophyll a was higher in the wild strain, and treatment samples had lower values in comparison to control samples. Epiphyte gametophytes possibly promoted reduction in pigment content of the tetrasporophytes on both strains. Wild strain samples without epiphyte gametophytes had higher photosynthetic efficiency. Epiphyte gametophytes produced cystocarps one week before free-living gametophytes. The amount of epiphyte gametophytes on tetrasporophytes is not different between strains. Epiphyte gametophytes were visible one week before on the wild strain than in the green variant strain. It was found that tetraspores give rise to epiphyte gametophytes through two distinct germination methods: outside or inside the thallus of the tetrasporophyte. Germination outside the tetrasporophyte thallus was more common, produced visible holdfasts and promoted cortex thickening in the cortical region of the tetrasporophyte. Germination inside the tetrasporophyte thallus did not show evidences of holdfasts nor cortex thickening on the tetrasporophytes. Epiphyte gametophytes holdfasts had adjacent cells to the cortex of the tetrasporophytes when they germinate outside the thallus; however, when germination occurred inside the thallus, the connection interface was closer to the medulla of the tetrasporophyte. Epiphyte gametophytes might represent a new life strategy that promotes sexual variability in a population mostly composed of tetrasporophytes. For cultivation purposes, wild tetrasporophytes with epiphyte gametophytes yielded more mass than the variant tetrasporophytes, being the best option for production. However, the green variant without epiphyte gametophytes produced more phycobiliproteins, making it a better option to harvest those substances / Gracilaria caudata J. Agardh é uma das espécies encontradas na costa brasileira que produzem ágar de boa qualidade. Em Rio do Fogo (RN), Brasil, uma linhagem variante verde de G. caudata foi descoberta em uma população composta principalmente por indivíduos de coloração vermelha (fenótipo selvagem). Gametófitos epífitos em tetrasporófitos foram observados para as duas linhagens. Considerando-se as linhagens selvagem e verde em condições controladas de laboratório, este estudo analisou: (i) os impactos dos gametófitos epífitos nos tetrasporófitos por meio de taxas de crescimento, conteúdo pigmentar e potencial fotossintetizante dos tetrasporófitos; (ii) o tempo necessário para a diferenciação de cistocarpos em gametófitos de vida livre e gametófitos epífitos; (iii) o número de gametófitos epífitos produzidos por tetrasporófito; e (iv) aspectos anatômicos da interseção entre tetrasporófitos e gametófitos epífitos. O experimento teve duração de 12 semanas. Amostras controle foram mantidas com seus gametófitos epífitos durante o experimento, enquanto as amostras tratamento tiveram seus gametófitos epífitos removidos semanalmente. Análises fisiológicas compararam amostras controle e tratamento, enquanto que para os estudos anatômicos utilizou-se apenas as amostras controle. A linhagem selvagem apresentou maiores taxas de crescimento que a linhagem verde nas duas primeiras semanas do experimento, quando ainda não estavam férteis; entretanto, após as doze semanas de cultivo, não foram observadas diferenças entre as linhagens tetrasporofíticas. A linhagem vermelha produziu tetrásporos com mais frequência do que a linhagem verde e apresentou deficiência em ficoeritrina e aloficocianina. As amostras tratamento da linhagem verde apresentaram valores maiores de aloficocianina e ficoeritrina do que às do controle. A linhagem selvagem apresentou menores teores de ficoeritrina e aloficocianina quando comparada à linhagem verde. As amostras tratamento da linhagem verde apresentaram maiores valores de aloficocianina, ficocianina e ficoeritrina que as amostras controle da mesma linhagem. A quantidade de clorofila a foi maior na linhagem selvagem, e as amostras tratamento desta linhagem apresentaram valores maiores que às do controle. A presença de gametófitos epífitos promoveu a redução no conteúdo pigmentar nas duas linhagens. Amostras tratamento da linhagem selvagem apresentaram potencial fotossintetizante maior do que amostras controle. A quantidade de gametófitos epífitos não foi diferente entre as linhagens. Gametófitos epífitos produziram cistocarpos uma semana antes do que gametófitos de vida livre. A linhagem selvagem produziu gametófitos epífitas uma semana antes da linhagem verde. A germinação de tetrásporos em tetrasporófitos ocorreu de duas maneiras: antes e após a liberação de tetrásporos. A liberação de tetrásporos seguida da germinação sobre o tetrasporófito foi mais frequente, produziu apressórios e promoveu aumento do número de células no córtex do tetrasporófito. A germinação de tetrásporos dentro do talo do tetrasporófito não apresentou evidências de apressórios ou espessamento da região cortical do tetrasporófito. A porção basal de apressórios de gametófitos epífitos permaneceu adjacente ao córtex do tetrasporófito. Quando a germinação do tetrásporo ocorreu ainda dentro do talo, a interface de conexão das células foi mais próxima da medula do tetrasporófito. Gametófitos epífitos podem representar uma nova estratégia de vida para a espécie por possibilitar a variabilidade por reprodução sexual em uma população predominantemente composta por tetrasporófitos. Para um possível cultivo em larga escala, tetrasporófitos com gametófitos epífitos da linhagem selvagem seriam mais adequados por produzirem mais massa que os da variante verde. Entretanto, se o objetivo for a produção de ficobiliproteínas, a linhagem verde seria a mais indicadaphycoerythrin and allophycocyanin. Green variant treatment samples had higher content of allophycocyanin, phycocyanin and phycoerythrin than the control samples. Chlorophyll a was higher in the wild strain, and treatment samples had lower values in comparison to control samples. Epiphyte gametophytes possibly promoted reduction in pigment content of the tetrasporophytes on both strains. Wild strain samples without epiphyte gametophytes had higher photosynthetic efficiency. Epiphyte gametophytes produced cystocarps one week before free-living gametophytes. The amount of epiphyte gametophytes on tetrasporophytes is not different between strains. Epiphyte gametophytes were visible one week before on the wild strain than in the green variant strain. It was found that tetraspores give rise to epiphyte gametophytes through two distinct germination methods: outside or inside the thallus of the tetrasporophyte. Germination outside the tetrasporophyte thallus was more common, produced visible holdfasts and promoted cortex thickening in the cortical region of the tetrasporophyte. Germination inside the tetrasporophyte thallus did not show evidences of holdfasts nor cortex thickening on the tetrasporophytes. Epiphyte gametophytes holdfasts had adjacent cells to the cortex of the tetrasporophytes when they germinate outside the thallus; however, when germination occurred inside the thallus, the connection interface was closer to the medulla of the tetrasporophyte. Epiphyte gametophytes might represent a new life strategy that promotes sexual variability in a population mostly composed of tetrasporophytes. For cultivation purposes, wild tetrasporophytes with epiphyte gametophytes yielded more mass than the variant tetrasporophytes, being the best option for production. However, the green variant without epiphyte gametophytes produced more phycobiliproteins, making it a better option to harvest those substances

Carotenoides são considerados substâncias bioativas e seu consumo tem sido associado à prevenção de doenças crônicas não transmissíveis. Os carotenoides com atividade pró-vitamínica atuam no combate à hipovitaminose A. O objetivo desta dissertação foi descrever a ingestão de carotenoides, destacando a contribuição do consumo fora do domicílio, de acordo com fatores socioeconômicos, demográficos e estado nutricional, além de identificar as principais fontes alimentares presentes na dieta da população brasileira. Utilizou-se como base de dados as informações integrantes do bloco de consumo alimentar pessoal, da Pesquisa de Orçamentos Familiares (POF 2008-2009), realizada pelo Instituto Brasileiro de Geografia e Estatística (IBGE), que envolveu 34.003 indivíduos com idade de 10 anos ou mais. Um banco de dados foi construído para viabilizar o cálculo das quantidades (médias) de carotenoides presentes na dieta dos participantes da amostra. Foram utilizadas principalmente informações contidas na base Nutrient Database for Standard Reference Release 23 - United States Department of Agriculture (USDA) e a Tabela Brasileira de Composição de Carotenoides em Alimentos. Foram elaboradas análises estatísticas descritivas envolvendo o cálculo de ingestão de carotenoides no domicílio e fora dele e as variáveis selecionadas. O consumo médio per capita foi de 4.117,0 &micro;g/dia para carotenoides totais e 2.337,9 &micro;g/dia para os pró-vitamínicos A. As maiores médias de ingestão de carotenoides (totais; pró-vitamínicos) foram identificadas entre os seguintes grupos: mulheres (4.245,8 &micro;g/dia; 2.458,9 &micro;g/dia), moradores do meio urbano (4.143,2 &micro;g/dia; 2.364,20 &micro;g/dia), habitantes da Região Sul (4.987,6 &micro;g/dia; 2.948,9 &micro;g/dia), idosos (4.694,3 &micro;g/dia; 2.853,8 &micro;g/dia), indivíduos com os maiores rendimentos (5.596,7 &micro;g/dia; 3.236,6 &micro;g/dia), com curso de pós-graduação completo (7.009,7 &micro;g/dia; 4.143,5 &micro;g/dia), de cor amarela (5.692,7 &micro;g/dia; 3.436,9 &micro;g/dia) e aqueles classificados com os maiores Índice de Massa Corporal - IMC (4.445,1 &micro;g/dia; 2.535,0 &micro;g/dia). Constatou-se que a contribuição fora do domicílio representou até ¼ da ingestão total de carotenoides. Observou-se que os indivíduos do sexo feminino, idade acima de 60 anos e obesos, embora ingerissem maiores quantidades destas substâncias, integraram os grupamentos que (em relação ao total) apresentaram menor participação na ingestão fora do domicílio. O crescimento da renda e da escolaridade foi fundamental para proporcionar níveis mais elevados de consumo. As principais fontes de carotenoides na dieta da população brasileira foram: salada, suco, alface, tomate, mamão, melancia, abóbora, batata-doce, cenoura, milho verde e ovo de galinha. Fora do domicílio prevaleceu a ingestão dos três primeiros alimentos/preparações. Os níveis de ingestão revelaram-se expressivamente inferiores aos preconizados como seguros. Medidas de incentivo ao consumo de frutas, verduras, legumes e seus derivados (fontes de carotenoides), sobretudo entre os jovens, são necessárias e prioritárias, especialmente com vistas à prevenção de doenças crônicas não transmissíveis e no combate à hipovitaminose A. / Carotenoids are considered bioactive substances and its consumption has been associated to prevention of chronic non communicable diseases. The carotenoids with pro-vitamin activity act against hypovitaminosis A. The aim of this dissertation was to report the carotenoids intake, highlighting the contribution of outof- home food consumption, accordingly with socioeconomic and demographical factors, nutritional status, also to identify the main food sources in the diet of Brazilian population. A secondary data from the 2008-2009 Household Budget Survey - POF - was used, published by the Brazilian Institute of Geography and Statistics (IBGE). The sample consisted of 34,003 study subjects (13,569 households), with at least 10 years-old. A database was built to allow the calculation of quantities (average) of carotenoids in the diet of study participants. Information was used primarily by the Nutrient Database for Standard Reference Release 23 - United States Department of Agriculture (USDA) and the Brazilian Table of Carotenoids Composition in Food. Descriptive statistical analysis was performed for calculation of carotenoid intake at home and out-of-home consumption. The average daily consumption per capita was 4,117.0 &micro;g/day for total carotenoids and 2,337.9 &micro;g/day for provitamin A carotenoids. The highest average intake of carotenoids (total; provitaminic) was found between the following groups: women (4,245.8 &micro;g/day; 2,458.9 &micro;g/day), urban dwellers (4,143.2 &micro;g/day; 2,364.20 &micro;g/day), South region population (4,987.6 &micro;g/day; 2,948.9 &micro;g/day), elderly people (4,694.3 &micro;g/day; 2,853.8 &micro;g/day), high-income individuals (5,596.7 &micro;g/day; 3,236.6 &micro;g/day), with full graduate degree (7,009.7 &micro;g/day; 4,143.5 &micro;g/day), yellow skinned person (5,692.7 &micro;g/day; 3,436.9 &micro;g/day) and those classified with highest Body Mass Index (BMI) (4,445.1 &micro;g/day; 2,535.0 &micro;g/day). The out-ofhome contribution found in this present study represented up to ¼ of the total intake of carotenoids. It was observed that individuals over 60 years, female and obese people, although ingested larger amount of these substances, belonged to the groups (in relation with total) which showed less interest in out-of-home eating. The increase in income and education was essential to provide higher levels of consumption. The main dietary carotenoids sources of Brazilian population were: salad, juice, lettuce, tomato, papaya, watermelon, pumpkin, sweet potato, carrot, corn and chicken egg. The consumption of first three food/preparation prevailed outside the home. The intake levels showed expressively lower than those recommended as safe. Policies to promote the consumption of fruits, vegetables and derived products (carotenoids sources) are necessary and priority, particularly among young people, especially aiming to prevent the risk of chronic diseases and combating hypovitaminosis A.

\'Piraroxa\' e \'Vanda\' são cultivares de alface cujos comportamentos pós-colheita ainda não foram caracterizados. Um dos diferenciais destas cultivares pode estar relacionado ao seu alto potencial antioxidante como resultado da ação de seus compostos fenólicos. A fim de avaliar os parâmetros pós-colheita e a viabilidade do uso destas cultivares como fontes de antioxidantes, o presente trabalho teve como objetivo investigar suas respostas fisiológicas e bioquímicas, comparando-as entre si em diferentes temperaturas de armazenamento e em épocas de colheita distintas. Tanto no verão quanto no inverno, as hortaliças foram armazenadas por 28 dias à 0ºC e 95-97%UR e por quatro dias em condição ambiente monitorada. Em todas as condições de armazenamento e períodos de colheita, não houve diferença entre as cultivares e tendências decrescentes foram observadas para a produção de etileno e as taxas respiratórias. O armazenamento refrigerado proporcionou acentuado declínio destas variáveis. Já em condição ambiente, na colheita de verão, a cv. Vanda apresentou produção superior de etileno e, na colheita de inverno, a cv. Piraroxa apresentou taxas respiratórias mais elevadas. Os parâmetros de coloração permaneceram constantes. As cultivares apresentaram tendências similares entre si, tanto para a perda de massa fresca quanto para o conteúdo de clorofila e carotenoides, e o armazenamento refrigerado e as altas umidades relativas mostraram-se eficazes para o controle da perda de massa. O conteúdo de antocianinas foi influenciado pela temperatura de armazenamento, mas não pela época de colheita, e não demonstrou estar diretamente relacionado ao potencial antioxidante da cv. Piraroxa. As características de qualidade representadas pela aparência das hortaliças foram preservadas, em armazenamento refrigerado, até o 28º dia e, em condição ambiente, até o primeiro e segundo dias. A atividade da polifenoloxidase (PPO) e o potencial antioxidante das hortaliças foram influenciados pela época de colheita, mas não pela temperatura de armazenamento. A cv. Vanda apresentou atividade da PPO superior na colheita de verão e a cv. Piraroxa apresentou potencial antioxidante superior em todas as condições de armazenamento e épocas de colheita. O teor de compostos fenólicos e a atividade sequestrante do radical livre DPPH apresentaram valores superiores na colheita de verão para ambas as cultivares, com tendências à constância de valores, enquanto o sistema-modelo ?-caroteno/ácido linoleico demonstrou tendências crescentes, com elevações significativas a partir do segundo dia de armazenamento em condição ambiente e a partir do 21º dia de armazenamento refrigerado. Os parâmetros fisiológicos analisados evidenciaram grande similaridade em relação ao comportamento pós-colheita das duas cultivares e a durabilidade e manutenção das características qualitativas das hortaliças durante o armazenamento refrigerado foi extremamente satisfatória. Em contrapartida, o armazenamento, tanto em condição ambiente monitorada quanto em refrigeração, não demonstrou constituir-se como técnica válida para a maximização do potencial antioxidante das hortaliças, embora a alface constitua fonte dietética importante de antioxidantes. / \'Piraroxa\' and \'Vanda\' are lettuce cultivars whose postharvest behavior has not yet been characterized. One of the differentials of these cultivars may be related to its high antioxidant potential as a result of its phenolic compounds action. In order to evaluate the postharvest parameters and feasibility of using these cultivars as sources of antioxidants, this study aimed to investigate their physiological and biochemical responses, comparing them to each other at different storage temperatures and at different harvest times. Vegetables were stored for 28 days at 0ºC and 95-97%RH and for four days at ambient monitored condition regardless of summer or winter seasons. In all storage conditions and harvest periods there was no difference between cultivars and decreasing trends were observed for ethylene production and respiratory rates. Cold storage provided dramatic decline of these variables. At ambient condition, however, cv. Vanda showed higher production of ethylene in the summer harvest and cv. Piraroxa had higher respiratory rates in the winter harvest. Color parameters remained constant. Cultivars showed similar trends among one another for both weight loss and the content of chlorophyll and carotenoids. Also, cold storage and high relative humidity were effective for the control of weight loss. Anthocyanins content was influenced by storage temperature, not by the harvest season, and did not show to be directly related to the antioxidant potential of cv. Piraroxa. Vegetables quality appeared to be preserved on cold storage until day 28, and at ambient condition until the first and second days. Polyphenol oxidase (PPO) activity and antioxidant potential of vegetables were influenced by harvest time, but not by the storage temperature. \'Vanda\' showed higher PPO activity in the summer harvest and \'Piraroxa\' showed higher antioxidant potential in all storage conditions and harvest times. Phenolic content and free radical scavenging activity of DPPH showed higher values in summer harvest for both cultivars, with constant value tendencies, while the model system ?-carotene/linoleic acid showed increasing trends, with significant increases in the second day of storage at ambient condition and after 21 days of refrigerated storage. The physiological parameters analyzed showed great similarity to postharvest behavior of the two cultivars, and the durability and maintenance of vegetables quality during refrigerated storage were extremely satisfactory. In contrast, both ambient and refrigerated monitored storages did not show as valid techniques for maximizing the antioxidant potential of vegetables, although lettuce constitutes an important source of dietary antioxidants.

Der Baikalsee ist der älteste, tiefste und größte (gemessen am Volumen) See der Welt, mit über 1500 endemischen Arten. Er wurde 1996 zum UNESCO Weltnaturerbe deklariert; doch auch dieses einzigartige Ökosystem könnte in Zukunft durch anthropogen bedingte Klimaänderungen und Nährstoff-Einträge gefährdet sein. Rezente und fossile Phytoplankton-Pigmente werden immer häufiger in Monitorings genutzt, um aktuelle und historische Änderungen der Phytoplankton-Produktivität und –Zusammensetzung zu bestimmen, welche Änderungen von klimatischen und anderen Umweltbedingungen anzeigen. Dennoch wurden im Baikal bislang keine rezenten und nur in wenigen Studien fossile Phytoplankton-Pigmente untersucht. Drei Hauptaspekte wurden in dieser Arbeit untersucht: (1) die Phytoplnkton und Phytoplankton-Pigment Verteilung in der euphotischen Zone, (2) deren Sedimentation zum Seeboden und Degradierung im oxischen Oberflächensediment, und (3) Änderung der fossilen Pigmente während des Holozäns (seit 10.000 Jahren) und der vorangegangenen Warmzeit (vor 129.000-117.000 Jahren). Schlussfolgernd läßt sich sagen, dass Pigment-basierte Analysen im Baikal verlässliche Aussagen über rezente und historische Phytoplankton-Variationen ermöglichen, welche durch Umwelteinflüsse (natürlichen oder menschlichen Ursprungs) induziert werden. Im Rahmen des EU-Projekts CONTINENT und des Langzeit-Monitorings der Staatlichen Universität Irkutsk werden die Ergebnisse zur Phytoplankton-Entwicklung seit der letzten Warmzeit bis zum Beginn des 21. Jahrhunderts den lokalen Naturschutz und globale Klimastudien unterstützen. / Lake Baikal is the World´s oldest, deepest and largest (by volume) lake and contains over 1,500 endemic species. Since 1996, after becoming a UNESCO World Heritage Area, the effects of global warming and local anthropogenic eutrophication on its unique ecosystem become a subject of international discussion. Recent and fossil phytoplankton pigments are being increasingly used to monitor recent and past responses of the phytoplankton composition and productivity to changes of climatic and other environmental conditions in aquatic systems. However, phytoplankton pigments were not yet investigated in the water column of Lake Baikal and only little in its sediment. Three main aspects were investigated in this thesis: (1) the distribution of phytoplankton and phytoplankton pigments in the euphotic zone, (2) its sedimentation through the water column and preservation within the oxidised surface sediment, and (3) variation of fossil phytoplankton pigments in the pristine lake during Holocene (since 10,000 years ago) and last interglacial (129,000-117,000 years ago). Taken together, pigment-based analyses were shown to accurately reflect phytoplankton variation caused by environmental changes of natural or human origin in Lake Baikal. In conjunction with the EU project CONTINENT and the long-term monitoring in Irkutsk, the phytoplankton development determined from the last interglacial up until the early 21st century will be used for future research of climate changes as well as for the Lake Baikal’s protection.