Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / During two seasons, samples were collected from two varieties of Vitis Vinifera Malbec and Syrah in a vineyard located in Itaara RS at different time of maturation. These grapes were crushed and subjected to two periods of maceration (7 an 14 days). From the moment of crushing until the end of the maceration samples were collected from the most every 48 hours, and analyses for Brix and pH at the time of sampling and further analysis of total polyphenols, anthocyanins and tannins were made after the freezing of the same. The wines produced were analyzed for acidity, pH, alcohol content, total polyphenols, anthocyanins and tannins. The aim was evaluate the influence of the harvest and maceration timing in the phenolic composition in wines from the varieties Malbec and Syrah produced in the central region of Rio Grande do Sul. Through the results allowed observing that as the grape has possibility of develops maturity, associated with a maceration time longer than 7 days, allows the production of wine more concentrated in phenolic compounds. The results show that the time of harvest, the maceration time, the weather conditions in the harvest and genetic factors in the studied grapes has influence in the phenolic composition of wines produced in this region. / Durante as safras de 2010 e 2011 foram coletadas amostras de duas variedades de Vitis vinifera Malbec e Syrah em um vinhedo localizado em Itaara-RS, em diferentes períodos de maturação. As uvas foram esmagadas e submetidas a dois tempos de maceração (7 e 14 dias). Foram coletadas amostras do mosto a cada 48 horas, desde o momento do esmagamento da uva até o momento da descuba. Para cada amostra, foram realizadas análises de Brix e pH no momento da amostragem e as demais análises de polifenóis totais, antocianinas e taninos foram realizadas posteriormente ao congelamento das mesmas. Os vinhos produzidos foram analisados quanto a acidez, pH, teor de álcool, polifenóis totais, antocianinas e taninos. O objetivo foi avaliar a influência que época de colheita e tempo de maceração tem sobre a composição fenólica dos vinhos produzidos na região central do Rio Grande do Sul. Através dos resultados permitiu-se observar que a medida que a uva tem a possibilidade de desenvolver a maturação, associado à um tempo de maceração superior a 7 dias há uma produção de vinhos mais concentrados em compostos fenólicos. Os resultados mostram que o momento da colheita, o tempo de maceração, as condições meteorológicas da safra e os fatores genéticos das uvas estudadas têm influência sobre a composição fenólica dos vinhos produzidos nesta região.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / O mercado de frutos regionais tem ganhado cada vez mais espaÃo no Brasil, tanto pela procura de alternativas por parte dos produtores, como pela busca de novas opÃÃes de frutas pelos consumidores. Dentre os frutos com alta prioridade para estudos e incentivos destaca-se o bacuri (Platonia insignis Mart.), por sua importÃncia econÃmica nas regiÃes Norte e Meio-Norte do Brasil. PorÃm, a alta consistÃncia da polpa de bacuri, causada pela elevada quantidade de polissacarÃdeos (pectina, hemicelulose, celulose e lignina) nos tecidos, impossibilita a difusÃo de seu nÃctar. Isto, aliado ao desconhecimento dos parÃmetros envolvidos no processamento do nÃctar de bacuri que dificulta a ampliaÃÃo da escala de produÃÃo. A maceraÃÃo da polpa de bacuri, por meio da aplicaÃÃo de enzimas com atividade pectinolÃtica, hemicelulolÃtica e celulolÃtica, permite a reduÃÃo da consistÃncia da polpa viabilizando a elaboraÃÃo do nÃctar de bacuri dentro dos padrÃes exigidos pelo MinistÃrio da Agricultura e do Abastecimento, por meio da InstruÃÃo Normativa nÂ12, de 4 de setembro de 2003 (mÃnimo 20 % de polpa). Assim, o objetivo geral do presente trabalho foi avaliar o processo de maceraÃÃo enzimÃtica da polpa de bacuri para obter um nÃctar adequado à comercializaÃÃo, bem como estudar a ampliaÃÃo da escala de produÃÃo desse nÃctar. O estudo teve inÃcio com a caracterizaÃÃo quÃmica e fÃsico-quÃmica, composiÃÃo dos compostos volÃteis, estrutura citoquÃmica e comportamento reolÃgico da polpa integral de bacuri. Em seguida, avaliou-se a reduÃÃo da consistÃncia da polpa de bacuri, por meio do estudo da maceraÃÃo enzimÃtica. Nesta etapa estudou-se a aplicaÃÃo das preparaÃÃes enzimÃticas comerciais Pectinex Smash XXL, Shearzyme 500 L, Pectinex Ultra SP-L, Viscozyme L e Celluclast na polpa de bacuri, bem como a influÃncia de parÃmetros como temperatura de incubaÃÃo (20 a 35 ÂC), tempo de incubaÃÃo (60 a 180 min), concentraÃÃo das preparaÃÃes enzimÃticas (53 a 267 μL.100gpolpa-1) e combinaÃÃes das preparaÃÃes enzimÃticas (Pectinex XXL e Celluclast; Viscozyme L e Celluclast) na eficiÃncia da maceraÃÃo. Na etapa seguinte identificou-se modificaÃÃes quÃmicas, fÃsico-quÃmicas, citoquÃmicas, cromatogrÃficas e reolÃgicas ocorridas na polpa de bacuri submetida à maceraÃÃo enzimÃtica. Em seguida, iniciou-se o estudo da influÃncia do perfil sensorial e a aceitabilidade do nÃctar de bacuri elaborado com polpa macerada enzimaticamente. Para esta etapa foram elaborados nÃctares com diferentes concentraÃÃes de polpa (10 e 20 %), sendo estas polpas maceradas em diferentes condiÃÃes. Finalmente avaliou-se a ampliaÃÃo da escala da produÃÃo do nÃctar de bacuri e a otimizaÃÃo da temperatura de pasteurizaÃÃo (80 a 120 ÂC) em pasteurizador tubular, atravÃs de fatores que influenciam direta ou indiretamente na qualidade do nÃctar. Os resultados das anÃlises fÃsico-quÃmicas e citoquÃmicas evidenciaram elevada consistÃncia da polpa de bacuri, em razÃo de quantidades considerÃveis de pectina, hemicelulose, celulose e lignina. Foram detectados 34 compostos volÃteis, sendo 15 terpenos, caracterizando-se como a principal classe de compostos volÃteis identificados na polpa integral de bacuri. O comportamento reolÃgico da polpa integral de bacuri foi caracterizado como nÃo-newtoniano pseudoplÃstico. A aplicaÃÃo da combinaÃÃo de 40 μL.100gpolpa-1 de Pectinex XXL e 100 μL.100gpolpa-1 de Celluclast atingiu maceraÃÃo enzimÃtica adequada na polpa de bacuri, reduzindo sua consistÃncia em, aproximadamente, 80,12 %. Os resultados de cromatografia revelaram que durante a maceraÃÃo enzimÃtica da polpa de bacuri houve aumento do nÃmero de compostos volÃteis. Em relaÃÃo Ãs anÃlises reolÃgicas, os ensaios oscilatÃrios mostraram que a polpa de bacuri macerada em duas condiÃÃes diferentes (aplicaÃÃo de 40 μL.100gpolpa-1 de Pectinex XXL e aplicaÃÃo de 100 μL.100gpolpa-1 de Celluclast; 40 μL.100gpolpa-1 de Viscozyme L e 100 μL.100gpolpa-1 de Celluclast) reduziram a viscoelasticidade da polpa de bacuri. As curva de escoamento apresentaram comportamento nÃo-newtoniano pseudoplÃstico da polpa de bacuri macerada enzimaticamente. AtravÃs das anÃlises sensoriais, foi possÃvel observar que a polpa de bacuri macerada em duas condiÃÃes diferentes (aplicaÃÃo de 40 μL.100gpolpa-1 de Pectinex XXL e 100 μL.100gpolpa-1 de Celluclast e aplicaÃÃo de 40 μL.100gpolpa-1 de Viscozyme L e 100 μL.100gpolpa-1 de Celluclast) conseguiram formular um nÃctar dentro dos padrÃes exigidos pela LegislaÃÃo Brasileira, com boa aceitaÃÃo e boa intenÃÃo de compra. O nÃctar de bacuri com 20 % de polpa, elaborado em escala piloto, nas condiÃÃes de 1:2 de polpa e Ãgua, maceraÃÃo enzimÃtica com aplicaÃÃo de 40 μL.100gpolpa-1 de Pectinex XXL e 100 μL.100gpolpa-1 de Celluclast, incubaÃÃo em reator de agitaÃÃo, 80 minutos de incubaÃÃo, temperatura de incubaÃÃo de 30 ÂC, agitaÃÃo de 200 rpm, pasteurizaÃÃo a 80 ÂC durante 15 segundos em pasteurizador tubular e envase assÃptico em capela, conseguiu obter seguranÃa microbiolÃgica sem afetar sua aceitaÃÃo e suas caracterÃsticas sensoriais perceptÃveis ao paladar do consumidor, alÃm de nÃo apresentar escurecimento.

A Uncaria tomentosa (Willd.) DC., comumente conhecida como unha de gato ou cat´s claw, é uma planta endêmica da Amazônia Peruana. Devido às suas propriedades terapêuticas, seus extratos e derivados são comercializados ao redor do mundo. As propriedades medicinais são atribuídas aos glicosídeos do ácido quinóvico, polifenois e especialmente aos alcalóides oxinólicos pentacíclicos. Assim, a mitrafilina é o principal alcalóide presente nos extratos da planta e, portanto, é o marcador químico de suas formulações comerciais. O processo de extração é uma etapa importante na padronização de seus extratos e, considerando a falta de estudos a respeito de sua influência sob o perfil fitoquímico, amostras de casca de unha de gato foram extraídas por meio de maceração dinâmica e extração assistida por micro-ondas. O objetivo desse estudo foi avaliar a influência dos fatores envolvidos no processo extrativo a respeito de sua composição química, atividade anti-inflamatória e antioxidante. Devido ao grande número de fatores de extração a serem avaliados, um planejamento experimental do tipo Placket Burman foi selecionado e os fatores escolhidos nessa etapa foram: porcentagem de planta em solvente, temperatura e tempo de extração. Adicionalmente, através de um planejamento Box Behnken, as condições ótimas de extração foram delineadas na segunda etapa do estudo. O tempo e a porcentagem de planta em solvente foram fatores significantes para a extração assistida por micro-ondas. Entretanto, o conteúdo de mitrafilina nesses extratos foi reduzido - comparativamente ao seu conteúdo total presente nas amostras analisadas - e, portanto, mais estudos são necessários para otimizar o seu rendimento. Além disso, o extrato otimizado foi avaliado quanto à capacidade anti-inflamatória, em um teste de edema de pata induzido por carragenina e apresentou uma capacidade inibitória na concentração de 0,57 mg de mitrafilina/ Kg de rato. Por conseguinte, tais achados confirmaram a sua atividade anti-inflamatória. Os resultados obtidos a partir da extração por maceração dinâmica sugerem que o alcalóide é facilmente extraído, pois não foi afetado por nenhuma das variáveis experimentais. Adicionalmente, os extratos apresentaram maior conteúdo de mitrafilina - comparativamente aos resultados observados na extração por micro-ondas. Entretanto, devido ao menor tempo empregado na extração assistida por micro-ondas, outros estudos são necessários a fim de otimizar a extração desse alcalóide por esse método. O extrato otimizado sob as condições de maceração dinâmica foi seco em spray drying e, utilizando um planejamento de mistura do tipo simplex-centroid, o efeito de diferentes misturas de três adjuvantes foi avaliado: Dmanitol, maltodextrina e Aerosil. Embora os extratos secos com Aerosil e maltodextrina tenham prevenido a degradação de mitrafilina - quando comparado ao extrato seco sem excipiente - a secagem resultou em elevada perda no conteúdo de alcalóide e também propriedades farmacotécnicas inadequadas. Tais observações sugerem que, mesmo em condições amenas de secagem, há a degradação do alcalóide. Portanto, tais resultados reforçam a necessidade de avaliações complementares a fim de prevenir a ocorrência de tais eventos / The Uncaria tomentosa (Willd.) DC. commonly known as unha-de-gato or cat´s claw is an endemic plant from the Peruvian Amazon. Due its therapeutic properties, the crude drug and a variety of extracts are commercialized worldwide. The healing properties are attributed to the glycosides of quinovic acid, polyphenols, and especially to the pentacyclic oxindole alkaloids. Thereby, mitraphylline is the main alkaloid present in the bark extract of U. tomentosa, and therefore, is the chemical marker of commercial formulations derived from the plant. The extraction process is an important step in the standardization of plant extract and considering the lack of studies that relate the influence of extractive processes in phytochemical profile of the cat´s claw extracts, the bark samples were extracted by dynamic maceration and microwave assisted extraction. The study aimed evaluate the influence of the extraction factors on the chemical composition, antioxidant and anti-inflammatory activities of the extracts from cat \'s claw barks. Due to the wide number of possible extraction factors to be evaluated and the lack of knowledge about the importance of this factor effects on U. tomentosa extract, the Placket Burman factorial design was selected and the experimental factors chosen in this step were: % plant solvent ratio, temperature and extraction time. Through a Box Behnken planning the optimal extraction conditions of cat´s claw bark will be outlined in the second stage of this work. The time and % plant solvent ratio were significant factors for microwave assisted extraction. However, the contents extracted of mitraphylline have been reduced - compared to the total yield of the plant - and, therefore, more studies are needed to optimize the alkaloid yield. The extract from the optimized conditions, was evaluated in carrageenan-induced rat paw oedema, and presented inhibitory capacity in concentration of 0.57 mg of mitraphylline / kg of rat. Therefore, these findings confirm its anti-inflammatory activity. The results obtained in the extractions by dynamic maceration, suggest that the alkaloid is easily extracted and is not affected by experimental variables. In addition, compared to microwave extraction, this methodology allowed extracts with higher content of mitraphylline. However, in view of the shorter extraction time employed in microwave extraction, other reviews are needed to increase the extraction of mitraphylline, by this method. The extract optimized by the conditions under dynamic maceration was dried in spray drying and using a simplex-centroid mixture design, the effect of different mixtures of three adjuvants - D- mannitol, maltodextrin and Aerosil- were evaluated. Although dried extracts with the aid of Aerosil and maltodextrin slightly prevented the degradation of mitraphylline - as compared to the dry extract without excipient - the drying process resulted in high loss in the total content of this alkaloid and inadequate physical properties. Such observation suggests that, even under the mild drying conditions, there is degradation of the alkaloid. Therefore, these results reinforce the need for auxiliary evaluations to prevent the occurrence of such events.

The effects of varying levels of sulphur dioxide (SO₂) on the cold maceration process was investigated with Pinot noir (Vitis vinifera L.) wine. The effects of these varying levels on the wines composition and colour parameters were examined. Cold maceration is a technique whereby grapes are crushed and placed at low temperatures (4 - lO°C) in the presence 50 - 150 mgL⁻¹ SO₂. This process is believed to provide a medium for the extraction of water soluble phenolic compounds, rather than the alcoholic extraction employed in normal fermentations. The extraction of these phenolic compounds was monitored from the juice through to six months of bottle age. The changes were measured using both Spectrophotometric and High Performance Liquid Chromatographic (HPLC) procedures. Cold maceration wines were found to be not significantly different to the control wine in all compositional parameters other than titrateable acidity which was found to be less than the control for all the cold maceration wines. The unsulphured cold maceration wine was not significantly different from the control wine in any of the spectral measurements except natural degree of ionisation, in which it was higher, and total phenolics, in which it was lower. These results indicate that the cold maceration process alone does not alter the extraction of phenolic compounds. The HPLC analysis of the wine confirmed the spectral results indicating that their were no significant differences in the levels of extraction of anthocyanins. The sulphured cold maceration wines were significantly greater than the control in visible colour, colour density, total anthocyanins, natural degree of ionisation, ionised anthocyanins and total phenolics. These results followed similar patterns with wine ageing, at six months these wines were still significantly greater in all the measurements apart from natural degree of ionisation. The results for the sulphured cold maceration wines indicates that SO₂ is acting as a solvent for the extraction of phenolic compounds including anthocyanins. The 50 mgL⁻¹ SO₂ cold maceration wine had similar colour and phenolic content to the 100 mgL⁻¹ SO₂ cold maceration wine at bottling, at six months the 50 mgL⁻¹ SO₂ cold maceration wine still retained a similar colour to the 100 mgL⁻¹ SO₂ cold maceration wine but had vastly reduced anthocyanin content. This indicates that for the grapes utilised in this study the most appropriate level of addition at cold maceration would be 50 mgL⁻¹ of SO₂. With grapes of differing phenolic content the level of addition required will vary.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Brazil is a major producer of paper, highlighted worldwide for producing and supplying the markets with large volumes of paper packaging, printing and writing paper and cardboard. Although the wood is the main source of raw material used in cellulose industries in Brazil, the use of non-timber fiber may be a satisfactory alternative for manufacturing of papers with different and special properties. In this sense, the objective of this study was to evaluate the productivity, morphology, anatomy and chemical composition of the fibers, as well as the properties of the pulps produced papers of Schoenoplectus californicus (C.A. Mey.) Soják (popularly known as reed), pure or mixed with eucalyptus pulp. We conducted chemical, morphological and productivity analysis. Thus the kraft pulping process and production roles in different treatments were performed. Through research and analysis, it can be noted that reed had low productivity and short fibers. Chemical analysis showed that the fibers have a high level of the reed extractives and silica, which makes it a favorable raw material for pulp production, on the other hand, the kraft pulping process resulted in reed pulp with low contents of hexenuronic acid suitable for the bleaching of pulp factor. The strength properties of the papers were negatively affected by the addition of reed pulp papers and the highest values of bulk and opacity were achieved with the lowest levels of refining of the pulps. It was concluded that reed did not show satisfactory for the production of papers of high strength characteristics. / O Brasil é um grande produtor de papel, destacando-se mundialmente por produzir e abastecer os mercados com expressivos volumes de papel de embalagem, papéis de imprimir e escrever e papel-cartão. Apesar de a madeira ser a principal fonte de matéria prima utilizada nas indústrias de celulose no Brasil, o emprego de fibras não madeireiras pode ser uma alternativa satisfatória para a fabricação de papéis com propriedades diferenciadas e especiais. Nesse sentido, o objetivo deste trabalho foi avaliar a produtividade, morfologia, anatomia e composição química das fibras, assim como as propriedades dos papéis produzidos de polpas celulósicas de Schoenoplectus californicus (C.A. Mey.) Soják (popularmente conhecido como junco), puros e misturados com polpa de eucalipto. Realizou-se análise química, morfológica e de produtividade. Desta forma foram realizados cozimentos pelo processo kraft e produção de papéis em diferentes tratamentos. Por meio das pesquisas e análises, pode-se constar que o junco apresentou baixa produtividade e fibras curtas. As análises químicas demostraram que as fibras de junco apresentam alto teor de extrativos e de sílica, o que o torna uma matéria prima desfavorável para a produção de polpa celulósica, por outro lado, o processo de polpação kraft do junco resultou em polpas com baixo teor de ácidos hexenurônicos, fator satisfatório para o branqueamento da polpa. As propriedades de resistência dos papéis foram afetadas negativamente pela adição de polpa de junco nos papéis e os mais altos valores de volume específico aparente e opacidade foram alcançados com os menores níveis de refino das polpas. Foi concluído que o junco não apresentou características satisfatórias para a produção de papéis de alta resistência.

<p>Fenolna jedinjenja su zaslužna za<br />osnovna senzorna svojstva srvenih vina,<br />pre svega boju i trpkost. Superoksid (O2^&bull;-) i hidroksil radikali (^&bull;OH) izazivaju<br />ozbiljna o&scaron;tećenja tkiva degradaciju<br />proteina, nerastvornih lipida, ugljenih<br />hidrata i nukleinskih kiselina. U ovom<br />radu ispitan je uticaj tehničkotehnolo&scaron;kih<br />uslova proizvodnje i odnosa<br />čvrste i tečne faze u kljuku, na boju vina,<br />sadržaj fenolnih jedinjenja i<br />antioksidativni potencijal. Izmena odnosa<br />čvrste i tečne faze u kljuku vr&scaron;ena je<br />vraćanjem jednog dela ili celokupne<br />količine &scaron;epurine i povećavanjem<br />sadržaja semenki dodavanjem 100, 200 i<br />300 % semenki u odnosu na prirodni<br />sadržaj. Stabilnost boje, sadržaja fenolnih<br />jedinjenja i antioksidativnog potencijala<br />ispitivana je pre i nakon tretmana vina sa<br />dva organska i dva neorganska sredstva<br />za bistrenje i stabilizaciju. Utvrđeno je da<br />povećanje sadržaja semenki u kljuku<br />pojačava antioksidatovno delovanje vina.<br />U vinu Cabernet sauvignon utvrđena je<br />vi&scaron;a vrednost antiradikalske aktivnosti<br />prema DPPH radikalima (AA_(DPPH&bull;)),<br />koja se nije promenila pod delovanjem<br />sredstava za bistrenje i stabilizaciju vina.<br />Vino Merlot ispoljilo je veću<br />antiradikalsku aktivnost na hidroksil<br />radikale (AA_(&bull;OH)).</p> / <p>Phenolic compounds are responsible for<br />basic sensory properties of red wines,<br />primarily color and astrigency.<br />Superoxide (O2^&bull;-) and hydroxyl radicals<br />(^&bull;OH) causes serious damage to the tissue<br />degradation of proteins, ansolubility<br />lipids, carbohydrates and nucleic acids.<br />The paper examined the impact of<br />technical and technological conditions of<br />production and relations of liquid and<br />solid phases in pomase on the color of<br />wine, phenolic compounds content and<br />antioxidant potential. Changing relations<br />between solid and liquid phases in<br />pomase carried out the return of a part, or<br />the whole amount of stem and increasing<br />seeds content adding +100, +200 and<br />+300 % of seeds. Color stability,<br />phenolic compounds content and<br />antioxidative potential was examined<br />before and after treatment of wine with<br />two organic and two inorganic agens for<br />fining and stabilization. It was found that<br />increasing the seeds content in pomase<br />increases antioxidative action of wines.<br />In the wine Cabernet Sauvignon was<br />found higher value antiradical activity to<br />DPPH radicals (AA_(DPPH&bull;)), which are not<br />changed under the fining action and<br />stabilization of wine. Merlot wine<br />exhibited a higher antioxidant potential<br />of the hydroxyl radicals (AA_(&bull;OH)).</p>

L’équilibre gustatif des vins secs repose notamment sur les saveurs amère et sucrée, dont les déterminants moléculaires n’ont été que partiellement élucidés. Un premier axe a consisté en l’étude de la contribution gustative des lignanes du chêne et neuf composés ont été observés pour la première fois dans le vin. Le (±)-lyonirésinol a été établi comme le plus amer et le plus abondant des lignanes isolés. Ses deux énantiomères ont été séparés, caractérisés par VCD et leur dégustation a révélé que seul le (+)-lyonirésinol possède une amertume modifiant le goût du vin. Dans un second axe, la saveur sucrée conférée par les raisins aux vins secs a été étudiée. Des expérimentations de vinification combinées à des outils sensoriels ont montré un gain de saveur sucrée au cours de la macération post-fermentaire à chaud et un effet des pépins de raisin sur le moelleux des vins secs. La mise en place d’un protocole de fractionnement d’extrait de pépins et de vin, par des techniques séparatives couplées à la gustatométrie, a permis la purification de six composés sapides. Plusieurs marqueurs de la sucrosité des vins secs ont ainsi été identifiés par FTMS et RMN : le mélange de deux nouvelles molécules, les acides 2-hydroxy-3-méthylpentanoïque-2-O-β-glucopyranoside et 2-hydroxy-4-méthylpentanoïque-2-O-β-glucopyranoside ; l’acide gallique-4-O-β-glucopyranoside et l’acide epi-DPA-3′-O-β-glucopyranoside, identifiés pour la première fois dans les vins, ainsi que l’ILA-Glc et l’astilbine. Ces nouveaux marqueurs ont été quantifiés dans les vins ainsi que dans les différentes parties de la baie pour préciser leur localisation et établir leur contribution gustative. / Dry wines taste balance is mainly based on bitter and sweet tastes, whose molecular determinants have been only partially explained. The first key objective was the study of the gustatory contribution of oak lignans. Nine compounds were identified in wines for the first time. (±)-lyoniresinol has been established as the bitterest and the most abundant of the isolated lignans. Its two enantiomers have been resolved, characterized by VCD and their tasting revealed that only (+)-lyoniresinol is bitter and modifies wine taste. In the second part of this work, the contribution of grapes to wine sweet taste has been studied. The combination between vinification experimentations and sensorial tools showed a gain of sweetness during a warm post-fermentative maceration as well as an influence of grape seeds on dry wine sweetness. A fractionation protocol of grape seeds macerates and wines has been established. Separation techniques coupled with gustatometry allowed the isolation of six taste active compounds. Several markers of dry wines sweetness have been identified by FTMS and NMR: the mix of two new compounds, 2-hydroxy-3-methylpentanoic-2-O-β-glucopyranoside and 2-hydroxy-4-methylpentanoic-2-O-β-glucopyranoside acids; gallic-4-O-β-glucopyranoside acid and epi-DPA-3′-O-β-glucopyranoside acid, identified for the first time in wines, ILA-Glc and astilbin. These new markers have been quantified in wines and in different parts of grape berry in order to refine their localization and to establish their gustatory contribution.

La liqueur Grand Marnier® produite par la Société des Produits Marnier-Lapostolle (SPML), contient un arôme d'orange amère. Cet arôme, appelé parfum, est obtenu à partir de l'huile essentielle (HE) d'écorces d'orange amère qui ont subi un procédé de macération-distillation. Le but de ce travail de thèse a été de cibler les composés d'arôme clés des écorces d'orange amère et de comprendre leur comportement au cours de la production du parfum, afin de trouver des stratégies d'optimisation. Les axes d'étude ont été les suivants : (1) identification des composés volatils odorants de l'HE et du parfum d'orange amère; (2) observation et compréhension des étapes de la production du parfum, des matières premières à la distillation, et étude de leur impact sur la qualité du parfum (3) étude détaillée de la distillation discontinue multi-étagée. Parmi les 51 et 37 composés volatils identifiés de l'HE et du parfum, nous avons détecté par olfactometrie 19 composés odorants dans l'HE et 7 dans le parfum. Avec les résultats de l'HE de l'axe (1), une sélection de composés d'arôme, dits marqueurs, a été faite selon certains critères. Cette procédure a été validée par une étude sensorielle de classification d'HE d'orange amère de différentes origines géographiques. Les observations et résultats de l'axe d'étude (2) ont montré que la distillation est l'étape de la production qui a le plus grand impact sur la qualité du parfum. Durant la distillation, 9 paramètres de conduite, tels que le titre alcoométrique volumique et le taux de reflux, ont été régulièrement enregistrés. En parallèle, les composés marqueurs ont été quantifiés dans des échantillons de distillat prélevés à des moments spécifiques de la distillation des têtes aux queues. La connaissance du comportement des composés marqueurs et de leurs propriétés physico-chimiques permet de mieux comprendre la conduite actuelle de la distillation. Ainsi des changements de paramètres de distillation ont été proposés et des essais pilote ont été mis en place dans l'axe d'étude (3). Dans l'optique de contrôler et d'optimiser la distillation discontinue multi-étagée, d'autres travaux ont été menés en simulation avec le logiciel BatchColumn de ProSim®. Cela nécessite de : 1) déterminer les données d'équilibre liquide-vapeur de certains composés marqueurs ; 2) trouver un modèle thermodynamique représentant les données expérimentales ; 3) intégrer les données expérimentales et le modèle choisi dans le logiciel BatchColumn. La distillation telle qu'elle est menée à la distillerie de la SPML a bien été représentée. De futures études, incluant des changements de paramètres tels que la composition de la charge du bouilleur, des paramètres de conduite et de structure pourront être réalisées, afin d'optimiser le procédé et voir l'impact de ces changements sur la qualité du parfum. / The Grand Marnier® liqueur produced by the Société des Produits Marnier-Lapostolle (SPML), is composed of a bitter orange aroma. This aroma, called parfum, is produced from essential oil (EO) of bitter orange peelings that underwent a maceration-distillation process. The aim of this PhD study was to focus on the key odour compounds of the bitter orange peelings, and understand their behaviours throughout the process, in order to find optimisation strategies. The following strategies were applied: (1) identification of odour volatiles compounds in bitter orange EO and parfum; (2) observation and understanding of the steps of the parfum production, from raw material to distillation, and study of their impacts on the quality of the parfum; (3) deep study of the multi-stage batch distillation. Among the 51 and 37 volatile compounds identified, we detected by olfactometry 19 odour compounds in EO and 7 in parfum. From the EO results of the strategy (1), a selection of odour compounds, called markers, was thus carried out applying specific filters. This procedure was validated by a classification sensorial study of bitter orange EO from different geographical origins. Observations and results of strategy (2) demonstrated that distillation has the biggest impact on the quality of the parfum. During distillation, 9 key process parameters, such as the alcoholic strength by volume and reflux rate, were continuously recorded. In parallel, markers compounds were quantified in distillate samples collected at specific control points from head to tail cuts. The behaviour of the key markers together the knowledge of their physical-chemical characteristics made it possible to better understand the current lead of the distillation. Thereby changes of distillation parameters were proposed and pilote trials were carried out in the strategy (3). In view to control and optimise the multi-stage batch distillation process, other works were focused on simulation with the BatchColumn software from ProSim®. This requires to: 1) determine the vapour-liquid equilibrium data of certain markers compounds; 2) build a thermodynamic model simulating real experimental data; 3) integrate the experimental data and the model selected in BatchColumn. With this approach, we easily represented the distillation as it was realised in the industry. Futures studies, including changes of parameters such as still composition, distillation and structure parameters, could be carried out to optimise the process and see the impact on these changes of the quality of the parfum.

This research investigated yeast populations and diversity during pre-fermentation cold maceration and alcoholic fermentation of Vitis vinifera L. cv. Pinot noir grapes from a commercial vineyard (Dayton, OR). Fermentations were conducted at the Oregon State University research winery in 100 L tanks while grapes from the same vineyard lot were fermented at a commercial winery. Samples were taken daily during pre-fermentation maceration (9°C) and alcoholic fermentation (27°C) and plated on WL and lysine media to determine Saccharomyces and non-Saccharomyces populations and diversity. Total non-Saccharomyces populations increased from 1 x 10³ cfu/mL to 1 x 10⁵ cfu/mL during pre-fermentation cold maceration and reached a maximum of 1 x 10⁷ cfu/mL during alcoholic fermentation. Thirteen distinct yeast species were tentatively identified based on appearance on WL media and were initially screened for β-glucosidase activity using 4-methyllumbelliferyl-β-D-gluconopyranoside (4-MUG) plates. The identity of the isolates screening positive for β-glucosidase activity was determined by sequence analysis of the D1/D2 domain of the 26S rDNA gene. The five isolates identified were Metschnikowia pulcherrima, Hanseniaspora uvarum, Kluveromyces thermotolerans, and two Saccharomyces cerevisiae isolates. β-glucosidase activity was further characterized and quantified using a liquid media representing grape must conditions (pH 3.5, 20° Brix) at two temperatures (25°C and 8°C). While increasing sugar concentration suppressed the β-glucosidase activity of H. uvarum (-99%), β-glucosidase activity still remained relatively high for M. pulcherrima, S. cerevisiae isolate 1, and S. cerevisiae isolate 2. At 8°C, β-glucosidase activity was reduced for M. pulcherrima compared to activity at 25°C, but activity increased for K. thermotolerans, S. cerevisiae isolate 1, and S. cerevisiae isolate 2. The yeast isolates possessing β-glucosidase activity were used in fermentations of Vitis vinifera L. cv. Pinot Noir grapes. The grapes were treated with high hydrostatic pressure (HHP) to inactivate naturally occurring yeast and bacteria. All yeast isolates grew during pre-fermentation cold maceration (7 days at 9°C) and populations increased 3 to 4 logs. Following pre-fermentation cold maceration, all ferments were warmed to 27°C and inoculated with S. cerevisiae RC212. Alcoholic fermentations were all complete within eight days and after pressing wines were analyzed for volatile aroma compounds by SPME-GC-MS. The presence of different yeast isolates during pre-fermentation cold maceration resulted in wines with unique aroma profiles. Ethyl ester concentrations were highest in the wine that did not undergo a pre-fermentation cold maceration, while concentrations of branch-chained esters were higher in the treatments with yeast present during pre-fermentation cold maceration. Pre-fermentation cold maceration with yeast isolates demonstrating β-glucosidase did not affect the concentration of β-damascenone or β-ionone. Wines that had undergone pre-fermentation cold maceration with S. cerevisiae isolate 1, S. cerevisiae isolate 2, and a combination of all isolates resulted in over twice the concentration of β-citronellol over wines that did not undergo a pre-fermentation cold maceration. / Graduation date: 2013

Les fruits et les sous-produits de l’industrie de transformation des fruits sont obtenus chaque année en quantités importantes partout dans le monde. Les cerises et les résidus de pommes sont parmi les sources végétales les plus riches en composés bioactifs qui sont reconnus pour leurs effets bénéfiques sur l’organisme humain. Des méthodes appropriées d’extraction (macération, extraction par solvant pressurisé, extraction assistée par ultrasons, extraction assistée par microondes), d’analyse (HPTLC, HPLC-UV-DEDL, HPLC-MS, SFC) et de fractionnement (CPC, HPLC semi-préparative, extraction liquide-liquide) ont été mises au point pour la récupération, l’identification et la purification des composés bioactifs de cerises (Prunus avium) et de résidus de différentes variétés de pommes (Royal Gala, Golden, Granny Smith, Pink Lady). Les résultats obtenus au cours des travaux de recherches indiquent le fait que ces sources végétales contiennent des composés phénoliques (cerises, résidus de pommes) et des composés triterpéniques (résidus de pommes) qui peuvent être valorisés par incorporation dans différentes formulations alimentaires, pharmaceutiques, cosmétiques etc. / Fruits and by-products of fruit processing industry are produced annually in large quantities worldwide. Cherries and apple pomace are among the richest plant sources in bioactive compounds that are recognized for their beneficial effects on the human body. Appropriated methods of extraction (maceration, pressurized solvent extraction, ultrasoundassisted extraction, microwave assisted extraction), analysis (HPTLC, HPLC-UV-ELSD, HPLC-MS, SFC) and fractionation (CPC, HPLC semipreparative, liquid-liquid extraction) have been developed in order to extract, to identify and to purify bioactive compounds of cherry (Prunus avium) and pomaces of different apple varieties (Royal Gala, Golden Delicious, Granny Smith, Pink Lady). The results obtained during the research work indicate that these plant sources contain phenolic compounds (cherry, apple pomace) and triterpenic compounds (apple pomace) that can be used as ingredients for various food, pharmaceutical, cosmetic formulations etc.