ABSTRACT A core tool of sensory science is the use of trained descriptive panels. This research describes an investigation into the role of motivation in the performance of trained panels and the use of a trained panel to develop a better understanding of the perception of Sauvignon blanc wines. Substantial investment in time and money is directed towards ensuring trained panels perform optimally. Having selected a panel, the panel leader needs to ensure that panellists provide accurate, reliable data. Panellist motivation is also an important factor to consider. While performance psychology, education and sport science fields have researched motivation extensively, knowledge about panellist motivation within sensory science is limited. However, findings from existing research in these other areas - which suggest an important role for autonomy, competence and relatedness - can be applied to sensory panels in order to increase intrinsic motivation. The initial part of the research investigated the fundamental factors that affect and influence panellists’ motivation and participation. A survey (n=74) revealed that extra income and a general interest in food were the key drivers in inspiring people to become panellists, whilst enjoyment in being a panellist, interest in food, and extra income were key drivers for people to remain panellists. In a second survey, the intrinsic motivation of seven trained panels from four countries (n=108) was assessed. External panels were found to be more intrinsically motivated than internal panels. Experienced panellists had an increased perception of competence, which is a key factor for people to be intrinsically motivated. Understanding motivational frameworks currently used in other research fields and integrating them into existing panel training protocols may enhance and sustain panellists’ intrinsic motivation. A trained panel (n=14) was then used in the second part of the thesis to identify key flavours in Sauvignon blanc wines from Australia, France, New Zealand, Spain, South Africa and USA. Sixteen characteristics were identified and measured, including sweet sweaty passionfruit, capsicum, passionfruit skin/stalk, boxwood/cat’s urine, grassy, mineral/flinty, citrus, bourbon, apple lolly/candy, tropical, mint, fresh asparagus, canned asparagus, stonefruit, apple and snowpea. Principal component analysis was used to describe differences between regions and countries. Sauvignon blanc wines from Marlborough, New Zealand (NZ), were described by tropical and sweet sweaty passionfruit characteristics, while French and South African Sauvignon blanc wines were described as having flinty/mineral and bourbon-like flavors. Chemical analyses of these wines also showed that Marlborough, NZ wines had more methoxypyrazine and thiol compounds. A consumer study (n=109) showed that New Zealanders significantly prefer New Zealand style Sauvignon blanc. The final part of this research focused on using trained panellists to explore the interactions between volatile and non-volatile wine compounds and their effects on the aroma profile of New Zealand Sauvignon blanc wine. Four volatile aroma compounds that are important in New Zealand Sauvignon blanc wine were studied (isobutyl methoxypyrazine [MIBP], 3-mercaptohexanol [3MH], 3-mercaptohexanol acetate [3MHA], and ethyl decanoate). Each of these four aroma compounds were assessed in combination with three non-volatile polyphenolic compounds commonly found in Sauvignon blanc wine: catechin, caffeic acid and quercetin. Results showed each polyphenol had a unique effect when blended with a specific aroma compound, either suppressing, accentuating, or showing little effect on the perception of the aroma compounds. The perception of MIBP, 3MH, and ethyl decanoate were largely suppressed by the added polyphenols, with a few exceptions. The perception of 3MH was accentuated with the addition of caffeic acid, and the perception of 3MHA was accentuated with the addition of catechin. The interactive effects of aroma compounds with polyphenols likely reflect non-covalent associations in the wine solution that reduce the volatility of the aroma compounds. With an understanding of the interactive effects of volatile and non-volatile compounds in wine, winemakers might optimize the impact of selected volatile compounds by managing polyphenol levels, supporting their efforts to attain desirable wine aroma profiles.

ABSTRACT A core tool of sensory science is the use of trained descriptive panels. This research describes an investigation into the role of motivation in the performance of trained panels and the use of a trained panel to develop a better understanding of the perception of Sauvignon blanc wines. Substantial investment in time and money is directed towards ensuring trained panels perform optimally. Having selected a panel, the panel leader needs to ensure that panellists provide accurate, reliable data. Panellist motivation is also an important factor to consider. While performance psychology, education and sport science fields have researched motivation extensively, knowledge about panellist motivation within sensory science is limited. However, findings from existing research in these other areas - which suggest an important role for autonomy, competence and relatedness - can be applied to sensory panels in order to increase intrinsic motivation. The initial part of the research investigated the fundamental factors that affect and influence panellists’ motivation and participation. A survey (n=74) revealed that extra income and a general interest in food were the key drivers in inspiring people to become panellists, whilst enjoyment in being a panellist, interest in food, and extra income were key drivers for people to remain panellists. In a second survey, the intrinsic motivation of seven trained panels from four countries (n=108) was assessed. External panels were found to be more intrinsically motivated than internal panels. Experienced panellists had an increased perception of competence, which is a key factor for people to be intrinsically motivated. Understanding motivational frameworks currently used in other research fields and integrating them into existing panel training protocols may enhance and sustain panellists’ intrinsic motivation. A trained panel (n=14) was then used in the second part of the thesis to identify key flavours in Sauvignon blanc wines from Australia, France, New Zealand, Spain, South Africa and USA. Sixteen characteristics were identified and measured, including sweet sweaty passionfruit, capsicum, passionfruit skin/stalk, boxwood/cat’s urine, grassy, mineral/flinty, citrus, bourbon, apple lolly/candy, tropical, mint, fresh asparagus, canned asparagus, stonefruit, apple and snowpea. Principal component analysis was used to describe differences between regions and countries. Sauvignon blanc wines from Marlborough, New Zealand (NZ), were described by tropical and sweet sweaty passionfruit characteristics, while French and South African Sauvignon blanc wines were described as having flinty/mineral and bourbon-like flavors. Chemical analyses of these wines also showed that Marlborough, NZ wines had more methoxypyrazine and thiol compounds. A consumer study (n=109) showed that New Zealanders significantly prefer New Zealand style Sauvignon blanc. The final part of this research focused on using trained panellists to explore the interactions between volatile and non-volatile wine compounds and their effects on the aroma profile of New Zealand Sauvignon blanc wine. Four volatile aroma compounds that are important in New Zealand Sauvignon blanc wine were studied (isobutyl methoxypyrazine [MIBP], 3-mercaptohexanol [3MH], 3-mercaptohexanol acetate [3MHA], and ethyl decanoate). Each of these four aroma compounds were assessed in combination with three non-volatile polyphenolic compounds commonly found in Sauvignon blanc wine: catechin, caffeic acid and quercetin. Results showed each polyphenol had a unique effect when blended with a specific aroma compound, either suppressing, accentuating, or showing little effect on the perception of the aroma compounds. The perception of MIBP, 3MH, and ethyl decanoate were largely suppressed by the added polyphenols, with a few exceptions. The perception of 3MH was accentuated with the addition of caffeic acid, and the perception of 3MHA was accentuated with the addition of catechin. The interactive effects of aroma compounds with polyphenols likely reflect non-covalent associations in the wine solution that reduce the volatility of the aroma compounds. With an understanding of the interactive effects of volatile and non-volatile compounds in wine, winemakers might optimize the impact of selected volatile compounds by managing polyphenol levels, supporting their efforts to attain desirable wine aroma profiles.

ABSTRACT A core tool of sensory science is the use of trained descriptive panels. This research describes an investigation into the role of motivation in the performance of trained panels and the use of a trained panel to develop a better understanding of the perception of Sauvignon blanc wines. Substantial investment in time and money is directed towards ensuring trained panels perform optimally. Having selected a panel, the panel leader needs to ensure that panellists provide accurate, reliable data. Panellist motivation is also an important factor to consider. While performance psychology, education and sport science fields have researched motivation extensively, knowledge about panellist motivation within sensory science is limited. However, findings from existing research in these other areas - which suggest an important role for autonomy, competence and relatedness - can be applied to sensory panels in order to increase intrinsic motivation. The initial part of the research investigated the fundamental factors that affect and influence panellists’ motivation and participation. A survey (n=74) revealed that extra income and a general interest in food were the key drivers in inspiring people to become panellists, whilst enjoyment in being a panellist, interest in food, and extra income were key drivers for people to remain panellists. In a second survey, the intrinsic motivation of seven trained panels from four countries (n=108) was assessed. External panels were found to be more intrinsically motivated than internal panels. Experienced panellists had an increased perception of competence, which is a key factor for people to be intrinsically motivated. Understanding motivational frameworks currently used in other research fields and integrating them into existing panel training protocols may enhance and sustain panellists’ intrinsic motivation. A trained panel (n=14) was then used in the second part of the thesis to identify key flavours in Sauvignon blanc wines from Australia, France, New Zealand, Spain, South Africa and USA. Sixteen characteristics were identified and measured, including sweet sweaty passionfruit, capsicum, passionfruit skin/stalk, boxwood/cat’s urine, grassy, mineral/flinty, citrus, bourbon, apple lolly/candy, tropical, mint, fresh asparagus, canned asparagus, stonefruit, apple and snowpea. Principal component analysis was used to describe differences between regions and countries. Sauvignon blanc wines from Marlborough, New Zealand (NZ), were described by tropical and sweet sweaty passionfruit characteristics, while French and South African Sauvignon blanc wines were described as having flinty/mineral and bourbon-like flavors. Chemical analyses of these wines also showed that Marlborough, NZ wines had more methoxypyrazine and thiol compounds. A consumer study (n=109) showed that New Zealanders significantly prefer New Zealand style Sauvignon blanc. The final part of this research focused on using trained panellists to explore the interactions between volatile and non-volatile wine compounds and their effects on the aroma profile of New Zealand Sauvignon blanc wine. Four volatile aroma compounds that are important in New Zealand Sauvignon blanc wine were studied (isobutyl methoxypyrazine [MIBP], 3-mercaptohexanol [3MH], 3-mercaptohexanol acetate [3MHA], and ethyl decanoate). Each of these four aroma compounds were assessed in combination with three non-volatile polyphenolic compounds commonly found in Sauvignon blanc wine: catechin, caffeic acid and quercetin. Results showed each polyphenol had a unique effect when blended with a specific aroma compound, either suppressing, accentuating, or showing little effect on the perception of the aroma compounds. The perception of MIBP, 3MH, and ethyl decanoate were largely suppressed by the added polyphenols, with a few exceptions. The perception of 3MH was accentuated with the addition of caffeic acid, and the perception of 3MHA was accentuated with the addition of catechin. The interactive effects of aroma compounds with polyphenols likely reflect non-covalent associations in the wine solution that reduce the volatility of the aroma compounds. With an understanding of the interactive effects of volatile and non-volatile compounds in wine, winemakers might optimize the impact of selected volatile compounds by managing polyphenol levels, supporting their efforts to attain desirable wine aroma profiles.

Cette thèse se divise en trois parties. La première concerne le développement d'une nouvelle voie d'accès à des hétérocycles azotés. Cette synthèse est basée sur deux étapes: l'addition radicalaire d'un xanthate, portant une fonction 1,2-dione, sur diverses oléfines suivie de sa condensation sur une diamine. Cette étude a permis de préparer des composés présentant un intérêt biologique certain tels que des pyrazines. De plus, une nouvelle méthodologie permettant l'accès à des structures imidazoles a été mise en évidence. La seconde partie a été consacrée à la préparation d'un support soluble à l'aide du procédé Madix. La dernière étude porte sur le développement de nouveaux agents modérateurs de la polymérisation radicalaire. Cette étude nous a amenés tout d'abord à synthétiser une large gamme de composés originaux de type dihydro-pyrazolone. Par la suite, la mise en place d'une étude modèle nous a permis de mesurer l'aptitude à se dissocier de ces composés puis de sélectionner les meilleurs candidats. Enfin, une étude poussée en polymérisation des agents sélectionnés a permis de mieux comprendre leur mécanisme d'action. Nous sommes en présence d'un système de type initer original. Ce système de polymérisation n'est cependant pas vivant du fait de l'irréversibilité de l'addition du contre radical dihydro-pyrazolone sur la chaîne polymère.

[ES] La presente tesis doctoral aborda el desarrollo de nuevos procesos catalíticos centrados en la valorización del glicerol, subproducto principal en la síntesis de biodiesel. El objetivo principal del trabajo consiste en utilizarlo como fuente de carbono para la producción de heterociclos nitrogenados de interés industrial, en concreto, para la producción de 2-metilpiperazina y 2-metilpirazina. Debido a la baja reactividad del glicerol y las drásticas condiciones de reacción que serían necesarias para llevar a cabo las transformaciones a estos heterociclos, se ha planteado como paso previo el estudio de la optimización y el entendimiento del proceso de deshidratación selectiva de glicerol a hidroxiacetona (o acetol). A través de la obtención de este compuesto intermedio, se han podido desarrollar procesos de producción de los heterociclos nitrogenados eficientes y selectivos, en condiciones de reacción moderadas. A este respecto, los precursores de hidrotalcitas del tipo Cu-Mg-Al dan lugar a una familia de materiales basados en óxidos mixtos Cu-Mg-Al capaces de llevar a cabo la deshidratación selectiva de glicerol a acetol en continuo con rendimientos del ¿40%. Además, estos catalizadores son estables durante más de 8 horas, mostrando también excelente capacidad de regeneración y reusabilidad. Del mismo modo, la combinación de centros ácido-base y redox exhibida por estos materiales ha permitido, a través de la combinación de estudios catalíticos y de caracterización, avanzar en el estado del arte en lo que respecta a la comprensión de esta reacción de deshidratación catalítica de glicerol. De esta forma, se ha podido comprobar el papel fundamental de las especies de Cu y, en concreto de las especies Cu(I) presentes en los catalizadores, en la generación de gliceraldehido como intermedio clave para la producción de acetol. Del mismo modo, los centros ácidos del catalizador facilitan la primera adsorción del glicerol, acelerando así la reacción. No obstante, la necesidad de alcanzar productividades de acetol más elevadas para asegurar el éxito de la estrategia global motivó el desarrollo y estudio, en este proceso de deshidratación selectiva de glicerol en continuo, de una segunda familia de catalizadores basados en óxido de cobre soportado sobre diferentes óxidos metálicos (SiO2, Al2O3 y ZrO2), combinando centros ácidos de Lewis y una alta exposición del Cu. La adecuada selección y optimización de estos materiales lleva a lograr, con varios de ellos, rendimientos del 60% a acetol con concentraciones de glicerol en la alimentación mucho más elevadas. Una vez establecidos varios sistemas catalíticos para la producción de acetol, se abordó la producción de los heterociclos nitrogenados de interés a partir de la combinación de esta molécula con etilendiamina. En concreto, el catalizador Pd/TiO2-Al2O3 tiene alta actividad específica hacia la formación de 2-metilpiperazina (80% de rendimiento), gracias a su elevada exposición de centros de Pd insaturados, crítica para activar el doble enlace C=N y así proceder a la hidrogenación de las iminas intermedias. En segundo lugar, el catalizador CuO/Al2O3-npw, muestra rendimientos del 50% a la 2-metilpirazina, siendo posible alcanzar valores cercanos al 60% cuando se usa el método de precipitación-deposición por micelas en fase reversa para incorporar las nanopartículas de CuO. Finalmente, se llevó a cabo una prueba de concepto para la síntesis de 2-metilpirazina a partir de glicerol en un reactor multi-lecho especialmente diseñado para realizar las dos etapas del proceso en "one-pot" con el mismo catalizador basado en CuO-soportado, obteniéndose resultados prometedores. En definitiva, se han establecido dos nuevas rutas catalíticas para la producción de heterociclos nitrogenados con glicerol como la principal fuente de carbono a través de su derivado acetol, abriéndose así nuevas perspectivas en el campo de la valorización sostenible de moléculas derivadas de biomasa. / [CA] La present tesi doctoral aborda el desenvolupament de nous processos catalítics centrats en la valorització del glicerol, subproducte principal en la síntesi de biodièsel, utilitzant-lo com a font de carboni per a la producció d'heterocicles nitrogenats d'interès industrial. En concret, per a la producció de 2-metilpiperazina i 2-metilpirazina. A causa de la baixa reactivitat del glicerol i les dràstiques condicions de reacció que serien necessàries per a dur a terme les transformacions a aquests heterocicles, s'ha plantejat com a pas previ un estudi detallat escometent l'optimització i l'enteniment del procés de deshidratació selectiva de glicerol a hidroxiacetona (o acetol). A través de l'obtenció d'aquest compost intermedi, s'han desenvolupat processos de producció dels heterocicles nitrogenats eficients i selectius, en condicions de reacció moderades. Referent a això, els precursors hidrotalcítics Cu-Mg-Al donen com a resultat una família de materials basats en òxids mixtos Cu-Mg-Al capaços de dur a terme la deshidratació selectiva de glicerol a acetol en continu amb rendiments del 40%. Així mateix, aquests catalitzadors són estables durant més de 8 hores, mostrant a més una excel·lent regenerabilitat i reusabilitat. De la mateixa manera, la combinació de centres àcid-base i redox exhibida per aquests materials ha permès, a través de la combinació d'estudis catalítics i de caracterització, avançar significativament en l'estat de l'art pel que fa a la comprensió d'aquesta reacció catalítica. D'aquesta manera, s'ha pogut comprovar el paper fonamental del Cu i, en concret del Cu(I), en la generació de gliceraldehid com a intermedi de reacció clau. Per altra banda, els centres àcids del catalitzador faciliten la primera adsorció del reactiu, accelerant així la reacció. No obstant això, la necessitat d'aconseguir productivitats de acetol més elevades per a assegurar l'èxit de l'estratègia global va motivar l'ús, en aquest procés de deshidratació selectiva de glicerol en continu, d'una segona família de catalitzadors basats en òxid de coure suportat sobre diferents òxids inorgànics d'alta àrea (SiO2, Al2O3 i ZrO2), combinant centres àcids de Lewis i una alta exposició del Cu. L'adequada selecció i optimització d'aquests materials aconsegueix, amb alguns d'ells, rendiments del 60% a acetol amb concentracions de glicerol en l'alimentació molt més elevades. Una vegada establits diversos sistemes catalítics per a la producció d'acetol, es va abordar la producció dels heterocicles nitrogenats d'interès a partir de la combinació d'aquesta molècula amb etilendiamina. En concret, el catalitzador Pd/TiO2-Al2O3 té una alta activitat específica cap a la formació de 2-metilpiperazina (80% de rendiment), gràcies a la seua elevada exposició de centres de Pd insaturats, crítica per a activar el doble enllaç C=N i així procedir a la hidrogenació de les imines intermèdies. En segon lloc, s'ha pogut comprovar que, en presència d'un catalitzador principalment àcid contenint Cu, és possible realitzar la dehidrociclació d'acetol amb etilendiamina per a obtindre 2-metilpirazina i altres alquilpirazinas. Concretament, el catalitzador CuO/Al2O3-npw, mostra rendiments del 50% a la 2-metilpirazina, sent possible aconseguir valors pròxims al 60% quan s'utilitza el mètode de precipitació-deposició per micel·les en fase revessa per a incorporar les nanopartícules de CuO. Finalment, es va dur a terme una prova de concepte per a la síntesi de 2-metilpirazina a partir de glicerol en un reactor multi-llit especialment dissenyat per realitzar les dues etapes del procés en "one-pot" amb el mateix catalitzador basat en CuO-suportat, amb resultats prometedors. D'aquesta manera, s'han establit dues noves rutes catalítiques per a la producció d'heterocicles nitrogenats amb glicerol com a la principal font de carboni, a través del seu derivat acetol obrint així noves perspectives en l'àmbit de la valorització sostenible de les molècules derivades de la biomassa. / [EN] This doctoral thesis addresses the development of new catalytic processes centered on glycerol valorization, which is the main by-product of biodiesel synthesis. In this sense, the main aim focused on using it as a carbon source to generate nitrogen heterocycles of industrial interest, specifically, to produce 2-methylpiperazine and 2-methylpyrazine. Due to the low reactivity of glycerol and the severe reaction conditions necessary to carry out the transformations towards these N-heterocycles, previous detailed research to optimize and understand the selective dehydration process of glycerol to hydroxyacetone (or acetol) was undertaken. Through obtaining this intermediate compound, it has been possible to develop efficient and selective nitrogen heterocycles production processes, under moderate reaction conditions. In this regard, Cu-Mg-Al hydrotalcite precursors give rise to a family of materials based on Cu-Mg-Al mixed oxides capable of carrying out the selective dehydration of glycerol to acetol continuously with yields of 40%. In addition, these catalysts are stable for more than 8 hours under operational conditions, showing excellent regeneration capacity and reusability. In the same way, through the combination of catalytic and characterization studies, the interesting mix of acid-base and redox centers exhibited by these materials has allowed for advancing significantly in the state of the art regarding understanding this glycerol catalytic dehydration reaction. Hence, it has been possible to verify the fundamental role of Cu species and, specifically, Cu(I) species present in the catalysts, in the generation of glyceraldehyde as a critical reaction intermediate for acetol production. Similarly, the acid centers of the catalyst facilitate the first adsorption of glycerol, thus accelerating the reaction. However, the need to achieve higher acetol productivities from glycerol to stand a chance to succeed in the overall strategy motivated the development and study of a second family of catalysts based on copper oxide supported on different metal oxides (SiO2, Al2O3 and ZrO2) combining Lewis acid centers and high Cu exposure. The proper selection and optimization of these materials lead to reaching, with several of them, yields of 60% to acetol with much higher glycerol concentrations in the starting feed. Once several catalytic systems had been established to produce acetol, the generation of the nitrogen heterocycles of interest from the combination of this molecule with ethylenediamine was investigated. Specifically, the Pd/TiO2-Al2O3 catalyst presents high specific activity when forming 2-methylpiperazine (80% yield). These excellent results could be attributed to the enhanced exposure of unsaturated Pd centers observed in this material, critical for activating the C=N double bond and thus proceeding to the hydrogenation of the intermediate imines. Secondly, the CuO/Al2O3-npw catalyst yields 50% to 2-methylpyrazine, reaching values close to 60% when the precipitation-deposition method by micelles in reverse phase is used to incorporate the CuO nanoparticles. Finally, a proof of concept of 2-methylpyrazine synthesis starting from glycerol by using a specially designed multi-bed catalytic reactor to perform the two-steps process in one-pot with the same CuO-supported catalyst was assayed, with promising results. In summary, two new catalytic routes have been established to produce nitrogen heterocycles with glycerol as the main carbon source through its derivative hydroxyacetone, thus opening new perspectives in the field of sustainable valorization of biomass-derived molecules. / Mazarío Santa-Pau, J. (2021). Catalytic transformations of glycerol via hydroxyacetone into nitrogen heterocycles of industrial interest [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/179915 / TESIS

This review summarizes the principles of cancer chemoprevention and discusses the evidence from epidemiologic and experimental studies and preclinical and clinical trials of potential colorectal chemopreventive agents. The putative mechanisms of action of the drugs in chemoprevention and their potential to reduce the incidence and mortality rate of colorectal neoplasms are discussed. The future of colorectal chemoprevention will depend on important new insights into molecular carcinogenesis of colorectal cancer, application of molecular markers as surrogate endpoints, and ultimately on therapeutic targets of prevention in clinical trials.

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