L’objectif de cette thèse était de réaliser des désodorisants, obtenus à partir de différentes essences naturelles. Ceux-ci doivent être efficaces dans l’amélioration du microclimat des atmosphères de travail. Une étude fondamentale sur l'optimisation de l'extraction des essences naturelles et l'identification des composants de ces essences a été réalisée par GC/MS. Nous avons étudié également les processus de reconnaissance moléculaire entre les composants majoritaires de ces essences et des CDs natives ou modifiées. La stabilité de ces complexes a été mesurée par trois méthodes différentes : l’headspace statique, la spectrophotométrie UV-visible et la microcalorimétrie de titration isotherme. La réalisation d’adsorbants à base de cyclodextrines a été effectuée en utilisant des polymères de cyclodextrine synthétisés à partir de l’épichlorhydrine ainsi que des matériaux hybrides de type CM-β-CD/LDH. L’efficacité des désodorisants obtenus a été évaluée en mesurant la durée de libération des composés odorants. / The objective of this thesis was to develop air fresheners from various natural essences. Those must be efficient in the improvement of working atmosphere microclimate. A fundamental study on the optimization of extraction of natural essences andidentification of components of these essences was performed by GC/MS. We have also studied the process of molecular recognition between the major components of these essences and native or modified CDs. The stability of these complexes was measured by three different methods: static headspace, UV-visible spectrophotometry and isothermal titration microcalorimetry.The realization of adsorbents supports based on cyclodextrins was carried out by using cyclodextrin polymers synthesized from epichlorohydrin and hybrid materials of CM-β-CD/LDH type. The efficiency of air fresheners was evaluated by measuring the release time of odorous compounds.

Two pre-fermentation treatments were investigated in Pinot noir (Vitis vinifera L.) wines. The effects of cold maceration and carbonic maceration on the wines' composition, colour parameters and sensory properties were examined. Cold maceration is a winemaking technique used to increase non-alcoholic extraction in Pinot noir winemaking prior to fermentation. It involves holding crushed grapes with approximately 100-150 mg l⁻¹ SO₂ at low temperatures and is thought to increase the colour, aroma and flavour of the resulting wines. Carbonic maceration uses whole bunches that have undergone anaerobic metabolism to produce characteristically fruity and spicy wines. Pre-fermentation cold maceration produces wines that are higher in titratable acidity and monomeric anthocyanin content, but lower in colour density, hue and polymeric pigments. Reducing the maceration temperature below 10°C has little effect. Carbonic maceration produces wines that are lower in titratable acidity, monomeric anthocyanin content, and colour density but are higher in colour hue and amount of polymeric pigments. Quantitative descriptive analysis was used to define the effects of these pre-fermentation maceration treatments on the sensory characteristics of the resulting wine. Trained panel members found that there were no discernable sensory differences in the compositional parameters despite measurable chemical differences. Investigation into the aroma and flavour characteristics of the wines found that carbonic maceration produces wines that were lower in berry aroma and higher in acetate or ester-type aromas than the control wines. These wines were considered to have specific raspberry, floral, sugar, cherry and chemical aromas. This chemical note was also observed in the flavour of the carbonic maceration wines. The temperature of the cold maceration process has no major effect on the aroma and flavour of the resulting wines. However, the 10°C maceration was higher in woody/tobacco aroma than the 4°C maceration, and the 10°C treatment was also higher in bitter flavour than all the other treatments. Cold maceration wines were found to have specific mixed berry, dried fruit and sweet-oxidised aroma characters, together with a blackberry flavour note.

A trial established in 2003 at Upper Moutere in Nelson, New Zealand, was used to evaluate the effect of mussel shells as reflective mulch on Vitis vinifera L. cv. Pinot noir vine performance and fruit and wine quality. Shell mulch had several effects on the environment and vine growth as well as grape and wine composition in the 2006/2007 season. Soil under mulch was cooler compared to un-mulched control, but buffered the extremes in temperatures. Fruiting zone temperature over shells was slightly higher during the day and cooler at night, showing no effect on mean hourly temperature. Shell mulch reflected greater amounts of UV-A, UV-B and PAR radiation into the fruiting zone. Shell reduced weed growth compared to control. Leaf petiole and blade samples showed higher amounts of calcium compared to control. Leaf SPAD values were higher in the shell treatment during veraison, previous and postharvest, but lower post budburst. While date of budburst was not affected by treatments, dates of flowering and veraison appeared to be slightly advanced over shells. Fruit set was similar between treatments and was considered poorer in shell bunches due to a larger population of seedless berries. Vine growth was not affected in terms of the number of nodes laid at pruning, flower cluster and shoot number pre shoot thinning, early shoot growth and lateral shoots development. Vigour was not increased by shells as demonstrated by pruning weights, canopy density and trunk circumferences being similar, though internode lengths in shell shoots were greater in 2007 and lower in 2006. Berry weights, bunch weights and vine yields were lower in shell than control, though greater berry numbers were recorded. There were slight differences between treatments in fruit and wine composition. Grape pH only varied in the middle of the sampling time, being higher the 2nd week and lower the 3rd week in shell grapes and TA was greater at harvest time. However, °Brix was only higher in shell grapes in the middle of the sampling period, being similar to control at veraison and harvest. Peduncle lignification was delayed at veraison as well as at harvest time. Shell must after crushing was greater in Brix but similar to control in pH and TA. Similarly, shell wines pre bottling showed higher alcohol and no differences for pH and TA. HPLC-DAD analyses of commercial-scale and microvin wines showed consistent differences of the individual flavonoid composition. Shell microvin wines were greater than control in quercetin and resveratrol. However, commercial shell wines were lower in epicatechin, gallic acid, resveratrol, and catechin than control. Leaf phenolic composition was also different between treatments. However, further analyses by HPLC-MS in wines as well as in leaves are necessary to identify individual compounds. Total anthocyanins and total phenolics were no different between treatments. Sensory analyses of microvin and commercial shell wines exhibited consistently lower levels of green and unripe tannins, and greater smoothness and complexity as well. Further analysis by GC-MS and HPLC-MS is warranted. Shell mulch improved sensory characteristics of the resulting wines.

The flavour or fragrance of Basmati rice is associated with the presence of 2-acetyl-1- pyrroline. This work shows that a gene with homology to betaine aldehyde dehydrogenase (BAD) has significant polymorphisms in the coding region of fragrant genotypes relative to non fragrant genotypes. Accumulation of 2-acetyl-1-pyrroline in fragrant rice genotypes may be explained by the presence of mutations resulting in loss of function of the fgr gene product. The fgr gene corresponds to the gene encoding BAD2 in rice while BAD1 is encoded by a gene on chromosome 4. Development of an allele specific amplification (ASA) based around the deletion in the gene encoding BAD2 allows, perfect, simple and low cost discrimination between fragrant and non-fragrant rice varieties and identifies homozygous fragrant, homozygous non-fragrant and heterozygous non-fragrant individuals in a population segregating for fragrance. The cDNAs transcribed from rice chromosomes 4 and 8, each encoding an enzyme with homology to betaine aldehyde dehydrogenase were cloned and expressed in E. coli. The enzyme responsible for fragrance, encoded from chromosome 8, had optimum activity at pH 10, showed low affinity towards betaine aldehyde (bet-ald) with Km value of approximately 63ìM but a higher affinity towards -aminobutyraldehyde (GABald) with a Km value of approximately 9ìM. The enzyme encoded from chromosome 4 had optimum activity at pH 9.5 and showed generally lower affinity towards most substrates compared to the enzyme encoded from chromosome 8, substrate specificities suggest that the enzymes have higher specificity to aminoaldehydes and as such both should be renamed as an aminoaldehyde dehydrogenase (AAD). The inactivation of AAD2 (BAD2) in fragrant rice varieties likely leads to accumulation of its main substrate GABald which then cyclises to 1-pyrroline the immediate precursor of 2AP.

Vineyards in New Zealand suffer bird damage caused by several avian species, including blackbirds and silvereyes. The introduced European Blackbird takes whole grapes which reduces yield. The self-introduced Australasian Silvereye pecks on grapes, leaving them on the vine to be further attacked by fungi and bacteria, and the subsequent off-odours can cause grapes to be refused by the winery or to suffer a price-reduction. Bird control methods remain primitive and largely ineffective during the long ripening period of wine grapes. An ecologically sound method to manage and reduce bird pressure requires deeper understanding of why some birds eat grapes, especially since grapes are not particularly nutritious. This work investigated the extent to which blackbirds and silvereyes are attracted by various compounds in ripening grapes. Since in natural grapes these compounds develop and change simultaneously, I developed an artificial grape in which a single parameter could be investigated. Artificial grapes (and sometimes nectar) were presented on a bird feeder table and the responses of birds to hexose sugars, the aromas 2-3-isobutylmethoxypyrazine and geraniol, tartaric and malic acids, grape tannins, and purple and green colour were recorded on timelapse video and analysed.

La presente tesi di dottorato ha riguardato la valutazione di differenti campioni di bentoniti sodiche. Le attività pianificate sono state indirizzate a comprendere l’interazione dei suddetti materiali con proteine a diverso peso molecolare naturalmente contenute nei vini bianchi. Ulteriori indagini hanno riguardato l’eventuale impatto delle argille testate sui composti aromatici di origine varietale e fermentativa dei mosti e/o dei vini. I risultati sottolineano il ruolo chiave esercitato dal “fattore matrice”: oltre al tipo di vino, prima di pianificare un trattamento di fining, devono essere considerate anche la tipologia e la dose di bentonite da utilizzare. / This PhD thesis dealt with the evaluation of different sodium bentonite samples. The planned activities were aimed to understand the interactions between bentonites and different molecular weight proteins naturally contained in white wines. Further investigations were related to the impact of the clays on varietal and fermentative aroma compounds of musts and/or wines. Results underscore the key role exerted by the “matrix factors”: bentonite dose and typology and wine style have to be carefully considered before planning a fining treatment.

Se ha estudiado el efecto del volumen de la barrica, el tostado y origen de la madera de roble y la tonelería sobre los parámetros cromáticos, aromáticos, sensoriales y nutricionales de vinos de Monastrell, Cabernet Sauvignon y Petit Verdot elaborados en la D.O. Jumilla. Los resultados han mostrado que los parámetros de la barrica afectan más a los aromas del vino y su caracterización sensorial que a los parámetros cromáticos y nutricionales. Los vinos de Monastrell envejecidos en barricas de menores volúmenes y mayor nivel de tostado presentan una mayor concentración de compuestos aromáticos, aunque son menos preferidos sensorialmente. Para la crianza de los vinos de Cabernet Sauvignon, la preferencia sensorial se ha correspondido con vinos envejecidos en barricas de volúmenes pequeños, de roble americano y tostado M+, donde aparecen mayores concentraciones de compuestos aromáticos, no aportando la tonelería diferencias muy grandes. Resultados similares se han encontrado en los vinos de Petit Verdot / The effect of barrel volume, toast level, oak wood origin and cooperage on chromatic, aromatic, sensory and healthy properties of Monastrell, Cabernet Sauvignon and Petit Verdot wines has been studied. The results have shown that Monastrell wines aged in the smallest barrels and with the highest toast level showed the highest aromatic compound concentrations although they were sensorially less preferred. The use of small American oak barrels, with M+ toast level for Cabernet Sauvignon ageing showed wines with the higher volatile compound concentrations and the better sensory properties. Similar results were observed in Petit Verdot wines. Chromatic properties and antioxidant capacity of the wines did hardly show any correlation with the different factors studied.

Las Bebidas con Aroma a Limón sufren cambios significativos con el paso del tiempo, que son asociados a deterioro por los consumidores. En la presente Tesis Doctoral se identificaron las causas de la inestabilidad de los Aromas de Limón. Para lograr la aparición de los defectos en forma acelerada se prepararon Bebidas con Aroma a Limón y se expusieron a alta temperatura. La identificación del defecto se realizó en primera instancia mediante técnicas de Evaluación Sensorial, conformando un Panel de Evaluadores Expertos, entrenados con Descriptores Sensoriales y una Rueda del Aroma Limón diseñados en este trabajo. Por otra parte se llevaron a cabo análisis de Cromatografía Gaseosa acoplada a Espectroscopía de Masas, para identificar los cambios químicos que experimentan los Aromas de Limón. La comparación de ambas metodologías presentó resultados que permitieron diseñar Aromas de Limón para uso en Bebidas, estables y con un alto nivel de aceptación por los consumidores. / Lemon Beverages experience significant changes over time, which are perceived as deterioration by consumers. This PhD thesis identifies the causes of Lemon Flavours instability. To achieve the quick appearance of the defects, Lemon Flavoured Beverages were prepared and exposed to high temperature. The identification of the defects was first performed by Sensory Evaluation techniques, training an Expert Panel of Evaluators, with tailor made Sensory Descriptors and a Lemon Flavour Wheel. Moreover analytical methods were performed using Gas Chromatography with Mass Spectroscopy, to identify the chemical changes experienced by Lemon Flavours. The comparison of both methodologies showed results that allowed the design Lemon Flavours to use in beverages, stable and with a high level of consumer acceptance.

En esta Tesis Doctoral se aplica la cromatografía de gases con detector olfatométrico (la nariz humana) en el análisis de los compuestos volátiles aromáticos de distintos alimentos: el vinagre de vino con Denominación de Origen Protegida “Vinagre de Jerez”, los pistachos tostados y el aceite de oliva. Los distintos métodos de preparación de muestra (la microextracción en fase sólida sobre el espacio de cabeza, o HS-SPME, y la extracción directa con disolvente, o DSE) han proporcionado extractos representativos del aroma de estos productos, y gracias a la técnica olfatométrica empleada (Aroma Extract Dilution Analysis o AEDA) se han identificado los odorantes más potentes. Así se ha logrado caracterizar el aroma de dichos alimentos, recogiéndose los resultados de las investigaciones realizadas en distintos artículos publicados en varias revistas internacionales. / In this Doctoral Thesis, the gas chromatography with olfactometry detector (the human nose) has been applied to analyse the volatile aromatic compounds from different foodstuffs: the wine vinegar produced under Protective Denomination of Origen “Vinagre de Jerez”, the roasted pistachios and the olive oil. The different sample pre-treatment methods employed (the headspace solid-phase microextraction, or HS-SPME, and the direct solvent extraction, or DSE) have provided representative aroma extracts from these products. Furthermore, and thanks to the olfactometric technique used (the Aroma Extract Dilution Analysis or AEDA), the most potent odorants have been identified. Thus, the aroma of all these foodstuffs has been characterized. All the results obtained from the research developed have been published in different international journals.

The flavour or fragrance of Basmati rice is associated with the presence of 2-acetyl-1- pyrroline. This work shows that a gene with homology to betaine aldehyde dehydrogenase (BAD) has significant polymorphisms in the coding region of fragrant genotypes relative to non fragrant genotypes. Accumulation of 2-acetyl-1-pyrroline in fragrant rice genotypes may be explained by the presence of mutations resulting in loss of function of the fgr gene product. The fgr gene corresponds to the gene encoding BAD2 in rice while BAD1 is encoded by a gene on chromosome 4. Development of an allele specific amplification (ASA) based around the deletion in the gene encoding BAD2 allows, perfect, simple and low cost discrimination between fragrant and non-fragrant rice varieties and identifies homozygous fragrant, homozygous non-fragrant and heterozygous non-fragrant individuals in a population segregating for fragrance. The cDNAs transcribed from rice chromosomes 4 and 8, each encoding an enzyme with homology to betaine aldehyde dehydrogenase were cloned and expressed in E. coli. The enzyme responsible for fragrance, encoded from chromosome 8, had optimum activity at pH 10, showed low affinity towards betaine aldehyde (bet-ald) with Km value of approximately 63ìM but a higher affinity towards -aminobutyraldehyde (GABald) with a Km value of approximately 9ìM. The enzyme encoded from chromosome 4 had optimum activity at pH 9.5 and showed generally lower affinity towards most substrates compared to the enzyme encoded from chromosome 8, substrate specificities suggest that the enzymes have higher specificity to aminoaldehydes and as such both should be renamed as an aminoaldehyde dehydrogenase (AAD). The inactivation of AAD2 (BAD2) in fragrant rice varieties likely leads to accumulation of its main substrate GABald which then cyclises to 1-pyrroline the immediate precursor of 2AP.