L'objectif premier de ce travail de thèse était de développer des analyses métabolomiques non ciblées de vins en bouteilles afin de déchiffrer les informations chimiques relatives à l’évolution de leurs compositions avec le temps. Cette recherche initiale était fondée sur l'hypothèse que, lors de l'analyse, les vins en bouteilles gardent une mémoire chimique des paramètres environnementaux à l’œuvre au moment de leur élaboration (gestion du vignoble, pratiques œnologiques, climat, terroir). Une seconde hypothèse reposait sur la nécessité d’étudier le passé pour anticiper l’évolution de la qualité du vin du point de vue de sa composition chimique. À cet effet et pour la première fois dans la science du vin, la Spectrométrie de Masse à Résonance Cyclotronique des Ions et à Transformée de Fourier (FTICR-MS), la Chromatographie Liquide couplée à la Spectrométrie de Masse (UPLC-Q-TOF-MS), la spectroscopie de Fluorescence d’Excitation et d’Émission (EEMF) et les statistiques multivariées ont été combinées. Le développement méthodologique a révélé l'avantage de coupler les mesures de masses exactes par FTICR-MS à la discrimination des isomères par UPLC-Q-TOF-MS afin d'étendre la gamme des métabolites détectables. Ces outils ont été appliqués à l'identification de marqueurs de vieillissement sur des séries verticales de vins rouges et blancs de Bourgogne, y compris sur des vins très anciens (millésimes inconnus) considérés comme des points extrêmes d'évolution, introduisant ainsi la notion de verticalomics. La caractérisation d'une série de vins blancs de Bourgogne (Chardonnay) a révélé que les espaces chimiques spécifiquement liés à des pratiques œnologiques (SO2 ajouté lors du pressurage, niveau de débourbage ou perméabilité du bouchon) pourraient être déchiffrés, bien que les signatures de millésimes étaient les plus significatives. Des expériences similaires sur les vins de Champagne (Chardonnay, et mélanges de Chardonnay, Pinot noir et Pinot Meunier) après la prise de mousse et le vieillissement sur lattes ont mis en évidence l'effet d'hormesis associé à l'oxygénation du vin. Enfin, les analyses non ciblées d'extraits de raisin et des vins correspondants provenant de différentes appellations et élaborés par le même vigneron ont révélé qu’il était possible de lire des signatures liées au terroir, en particulier après quelques années de vieillissement en bouteille. Plus largement, nos résultats fournissent une description globale sans précédent de la composition chimique du vin et de sa modification par le vieillissement. / The main objective of this work was to develop non-targeted metabolomics analyses of bottled wines in order to decipher chemical informations from the time-related evolution of their composition. This original research was based on the hypothesis that, when analyzed, bottled wines would still hold chemical memories of envionmental parameters (vineyard management, oenological practices, climate, terroir…) at the moment of their elaboration, even after several years of ageing. A second hypothesis was that in order to anticipate the future evolution of the wine quality in terms of chemical composition, it is necessary to know what it was in the past. To that purpose, and for the first time in wine science, Fourier Transform Ion Cyclotron Resonance – Mass Spectrometry (FTICR-MS), Liquid Chromatography coupled with mass spectrometry (UPLC-Q-ToF-MS), Excitation Emission Matrix Fluorescence (EEMF) and multivariate statistics were used in combination. Methodological develoments revealed the advantage of coupling exact mass measurements by FTICR-MS to isomeric discrimination by UPLC-Q-ToF-MS in order to extend the range of detectable metabolites. Such tools were applied to the identification of ageing markers in vertical series of red and white wines from Burgundy, including very old wines (unknown vintages) considered as evolution end points, thus introducing the concept of verticalomics. The characterization of series of white wines from Burgundy (Chardonnay) revealed that chemical spaces specifically related to eonological practices (SO2 addition at pressing, settling level, and permeability of the stopper) could indeed be deciphered although the vintage signatures were confirmed to be the most significant. Similar experiments on Champagne wines (Chardonnay, and blends of Chardonnay, Pinot noir and Pinot Meunier) after the "prise de mousse" and the ageing "sur lattes" further highlighted the hormesis effect associated with the oxygenation of wine. Finally, non-targeted analyses of series of grape extracts and corresponding wines from different appelations – though elaborated by the same winemaker – revealed that terroir-related signatures could be indeed read in wines, in particular after a few years of bottle ageing. Altogether our results provide an unprecedented comprehensive description of the chemical composition of wine and its modification through ageing.

Submitted by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2015-02-27T13:30:30Z No. of bitstreams: 5 11.pdf: 692915 bytes, checksum: 5a72c30d2db22b8d986fa5ff6134c4b8 (MD5) license_url: 49 bytes, checksum: fd26723f8d7edacdb29e3f03465c3b03 (MD5) license_text: 20904 bytes, checksum: e09bf99e64678e4285abf3ef3e05412d (MD5) license_rdf: 23422 bytes, checksum: b145eda3d84bdc4f56b389c0ab98d368 (MD5) license.txt: 2109 bytes, checksum: aa477231e840f304454a16eb85a9235f (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2015-02-27T14:36:27Z (GMT) No. of bitstreams: 5 11.pdf: 692915 bytes, checksum: 5a72c30d2db22b8d986fa5ff6134c4b8 (MD5) license_url: 49 bytes, checksum: fd26723f8d7edacdb29e3f03465c3b03 (MD5) license_text: 20904 bytes, checksum: e09bf99e64678e4285abf3ef3e05412d (MD5) license_rdf: 23422 bytes, checksum: b145eda3d84bdc4f56b389c0ab98d368 (MD5) license.txt: 2109 bytes, checksum: aa477231e840f304454a16eb85a9235f (MD5) / Made available in DSpace on 2015-02-27T14:36:27Z (GMT). No. of bitstreams: 5 11.pdf: 692915 bytes, checksum: 5a72c30d2db22b8d986fa5ff6134c4b8 (MD5) license_url: 49 bytes, checksum: fd26723f8d7edacdb29e3f03465c3b03 (MD5) license_text: 20904 bytes, checksum: e09bf99e64678e4285abf3ef3e05412d (MD5) license_rdf: 23422 bytes, checksum: b145eda3d84bdc4f56b389c0ab98d368 (MD5) license.txt: 2109 bytes, checksum: aa477231e840f304454a16eb85a9235f (MD5) Previous issue date: 2010 / Funda??o de Amparo ? Pesquisa do estado de Minas Gerais (Funda??o de Amparo ? Pesquisa do estado de Minas Gerais (FAPEMIG) / O presente estudo teve como objetivo avaliar o efeito da cianamida hidrogenada e a fenologia de produ??o em cultivares Pinot Meunier e Pinot Noir no munic?pio de Diamantina/MG. Os experimentos foram conduzidos em propriedade comercial localizada em Diamantina/MG. O vinhedo foi instalado em 2005 com as cultivares Pinot Meunier e Pinot Noir, enxertadas sobre o porta-enxerto 1103 Pausen, implantado com espa?amento de 1 m entre plantas x 2,5 m entre fileiras. As plantas foram conduzidas com 2 hastes em esquema de espaldeira vertical e tr?s fios de arame. A poda foi realizada em 4 de setembro de 2008, deixando uma haste curta com duas gemas por espor?o. Para a caracteriza??o fenol?gica foram feitas observa??es visuais a cada dois dias da poda at? a colheita. As demandas t?rmicas foram calculadas a partir de temperaturas observadas na Esta??o Meteorol?gica de Diamantina/MG. Para as curvas de matura??o foi utilizado suco para avalia??o qu?mica dos teores de s?lidos sol?veis totais (SST), acidez total titul?vel (ATT) e rela??o SST/ATT. Para avaliar o efeito da aplica??o de cianamida hidrogenada na brota??o, in?cio de matura??o e nas caracter?sticas f?sico-qu?micas das cultivares Pinot Meunier e Pinot Noir cultivadas em Diamantina/MG, foram realizadas avalia??es das plantas a cada dois dias, quando foram aferidas as porcentagens de brota??o e porcentagens de bagas em in?cio de matura??o. Na colheita foi realizada a contagem do n?mero de cachos por planta e foram amostradas 15 bagas por parcela para as seguintes avalia??es f?sico-qu?micas das bagas: umidade, massa, di?metros longitudinal (DL) e transversal (DT), rela??o DL/DT, teor de s?lidos sol?veis totais (SST), acidez total titul?vel (ATT), rela??o STT/ATT, a??cares redutores, antocianinas, flavon?ides, compostos fen?licos e pH. Os resultados obtidos demonstram dura??o do per?odo fenol?gico para as cultivares Pinot Meunier e Pinot Noir de 145 e 155 dias, respectivamente, para a produ??o da safra de ver?o em Diamantina/MG, podendo considerar a variedade Pinot Meunier de ciclo precoce. A exig?ncia t?rmica necess?ria para a produ??o da Pinot Meunier da poda ? colheita foi de 1340,67 GD e da Pinot Noir de 1446,95 GD. A cultivar Pinot Noir apresentou maior teor de s?lidos sol?veis totais e acidez, sendo a maior rela??o SST/ATT da Pinot Meunier nas condi??es de Diamantina/MG. Foram evidenciados para o efeito da aplica??o da cianamida hidrogenada a antecipa??o do in?cio da matura??o em 17 dias para a Pinot Meunier, a maior porcentagem de cachos em in?cio de matura??o em 45,84% e 28,23% para ?Pinot Meunier? e ?Pinot Noir?, respectivamente, e o incremento de algumas caracter?sticas f?sico-qu?micas avaliadas, como acidez total titul?vel, rela??o SST/ATT, flavon?ides e taninos para a cultivar Pinot Meunier e s?lidos sol?veis totais, a??cares redutores e umidade das bagas para a cultivar Pinot Noir. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Produ??o Vegetal, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2010. / ABSTRACT This study aimed to evaluate the effect of hydrogenated cyanamide and phenology of production in Pinot Meunier and Pinot Noir cultivars in Diamantina/MG.?The experiments were conducted in commercial property located at Diamantina/MG.?The vineyard was established in 2005 with the Pinot Meunier and Pinot Noir cultivars, grafted on rootstock Pausen 1103, deployed with a spacement of 1 m between plants and 2.5 m between rows.?The plants were conducted with 2 rods in an arrangement of vertical cordon and three wires.?The pruning was performed on September 4, 2008 leaving a short stem with two buds per spur.?To characterize the phenology were made visually observations every two days from pruning to harvest.?The thermal demands were calculated from the observed temperatures at the meteorological station of Diamantina/MG.?For the maturation curves was used a juice to make chemical evaluation of total soluble solids (TSS), total titratable acidity (TTA) and the TSS/TTA ratio.?To evaluate the effect of hydrogenated cyanamide on sprouting, early maturation and the physicochemical characteristics of the Pinot Meunier and Pinot Noir cultivars grown in Diamantina/MG where the assessments of plants were made every two days, then there were measured the percentage of budding?and the percentage of berries in early maturation.?At harvest it was counted the number of clusters per plant and there were sampled 15 berries per plot for the following physicochemical evaluations of berries: humidity, mass, longitudinal diameter (DL) and transversal diameter (TD), LD/TD ratio content of?total soluble solids (TSS), total titratable acidity (TTA), TSS/ATT ratio, reducing sugars, anthocyanins, flavonoids, phenolic compounds and pH.?The results show that the duration of phenological period for the Pinot Noir and Pinot Meunier cultivars are from 145 to 155 days, respectively, for the production of summer crops in Diamantina/MG, which may consider the Pinot Meunier variety in early maturity.?The thermal requirement needed for the production of Pinot Meunier from pruning to harvest was 1340.67 GD and Pinot Noir presented 1446.95 GD.?Pinot Noir cultivar showed the highest content of total soluble solids and acidic, and also the highest TSS/TTA ratio of Pinot Meunier in the Diamantina/MG environment.?For the purpose of applying hydrogenated cyanamide there were evidenced the anticipation of early maturation in 17 days for Pinot Meunier, the highest percentage of early-ripening in 45.84% and 28.23% for Pinot Meunier and Pinot Noir, respectively and the increment of some physicochemical characteristics evaluated as total titratable acidity, TSS/TTA ratio, flavonoids and tannins for the Pinot Meunier cultivar and total soluble solid, reducing sugars and humidity from the berries to the Pinot Noir cultivar.