The objective of the research described in this thesis has been to improve the toughness of phenolic networks while maintaining flame resistance. A four step synthetic scheme has been developed to prepare 4,4′-Bis(3,4-dicyanophenoxy)biphenyl(biphenoxyphthalonitrile). A 700 g mol-1 novolac oligomer was cured with relatively low concentrations of this reagent (~20 wt %) into high Tg (~190 °C) networks. The curing reaction was attrubuted to nucleophilic attack of the phenolic hydroxyl on the nitrile groups of the phthalonitrile resulting in the formation of heterocylic rings. TGA and cone calorimetry demonstrated that these networks have excellent thermo-oxidative stability. Further goals were to develop halogen-free, flame retardant monomers for improving the thermo-oxidative resistance of polystyrene and dimethylacrlyate/styrene(vinyl ester) networks. 4-Vinylphenoxyphthalonitrile, a phthalonitrile derivative of styrene, was synthesized. FTIR has been utilized to demonstrate this new monomer co-cured into vinyl ester networks in free radical thermosetting polymerizations. Upon post-curing the networks between 200-260 °C for ~1.5 h, the nitrile groups reacted to form heterocyclic crosslinks. TGA and cone calorimetry demonstrated that the 4-vinylphenoxyphthalonitrile substantially improved the flame resistance of vinyl ester networks. Copolymerizations of styrene and 4-vinylphenoxyphthalonitrile were conducted at 75 °C for 24 h using 0.5 wt % AIBN in chlorobenzene. Dynamic TGA at 10 °C min-1 in air showed that copolymers containing 10 and 25 mole % of 4-vinylphenoxyphthalonitrile had increased initial weight loss temperatures in air by (~50 °C higher) and increased the char yield between 400-600 °C. High molecular weight nitrile-functional, (hexafluoroisopropylidene)diphenol based aromatic poly(arylene ether)s with pendent sulfonic acid groups were prepared by nucleophilic step copolymerization of 4,4′-(hexafluoroisopropylidene)diphenol, 2,6-dichlorobenzonitrile, and 3,3′-disulfonate-4,4′-dichlorodiphenylsulfone under basic conditions in N-methyl-2-pyrrolidinone at 200 °C. A series of these materials with systematically varied concentrations of the sulfonic acid moieties showed increased glass transition temperatures, proton conductivities, and hydrophilicities as a function of disulfonation. Atomic force microscopy (AFM) demonstrated that the acidified copolymer with 35 mole % of disulfonated units was phase separated into a co-continuous morphology of hydrophobic and hydrophilic domains. / Ph. D.

Yes / The Forkhead transcription factor, FoxO3a induces genomic death responses in neurones following translocation from the cytosol to the nucleus. Nuclear translocation of FoxO3a is triggered by trophic factor withdrawal, oxidative stress and the stimulation of extrasynaptic NMDA receptors. Receptor activation of phosphatidylinositol 3-kinase (PI3K)-Akt signalling pathways retains FoxO3a in the cytoplasm, thereby inhibiting the transcriptional activation of death-promoting genes. We hypothesized that phenolic antioxidants such as tert-Butylhydroquinone (tBHQ), which is known to stimulate PI3K-Akt signalling, would inhibit FoxO3a translocation and activity. Treatment of cultured cortical neurones with NMDA increased the nuclear localization of FoxO3a, reduced the phosphorylation of FoxO3a, increased caspase activity and up-regulated Fas ligand expression. In contrast the phenolic antioxidant, tBHQ, caused retention of FoxO3a in the cytosol coincident with enhanced PI3K- dependent phosphorylation of FoxO3a. tBHQ-induced nuclear exclusion of FoxO3a was associated with reduced FoxO-mediated transcriptional activity. Exposure of neurones to tBHQ inhibited NMDA-induced nuclear translocation of FoxO3a, prevented NMDA-induced up-regulation of FoxO-mediated transcriptional activity, blocked caspase activation and protected neurones from NMDA-induced excitotoxic death. Collectively, these data suggest that phenolic antioxidants such as tBHQ oppose stress-induced activation of FoxO3a and therefore have potential neuroprotective utility in neurodegeneration.

Le règne végétal est une ressource renouvelable d'une large gamme de métabolites secondaires biologiquement actifs. Ces travaux de thèse proposent une stratégie multidisciplinaire d'évaluation du potentiel de composés phénoliques antimicrobiens d'origine végétale pour la conservation des aliments. Un criblage de l'activité antimicrobienne in vitro vis-à-vis de 8 souches de la flore pathogène et d'altération des aliments d'une centaine de molécules pures et une soixantaine d'extraits végétaux a d'abord permis de sélectionner les plus actifs. Différents mécanismes d'action vis-à-vis de S. aureus ont pu être mis en évidence par cytométrie de flux couplée à l'utilisation de marqueurs de l'état physiologique des bactéries pour quelques uns des composés actifs sélectionnés. En vue d'une application à de la viande bovine, l'activité antibactérienne des composés phénoliques ou extraits végétaux les plus actifs a été réévaluée dans des milieux de culture plus complexes mimant leur teneur en protéines et en matières grasses. Les résultats de ce criblage et un suivi microbiologique de viande hachée de bœuf avec 1% (m/m) d'extrait ajouté ont permis d'observer que les pertes d'activité antibactérienne observées étaient notamment corrélées aux interactions des composés phénoliques avec les protéines ou les matières grasses. L'incorporation des composés phénoliques ou extraits végétaux dans des matériaux d'emballage en contact alimentaire a constitué la seconde voie de mise en œuvre envisagée. Des films plastiques conservant une activité antibactérienne ont ainsi pu être élaborés par voie fondue / The plant kingdom is a renewable resource of a wide range of biologically active secondary metabolites. This thesis proposes a multidisciplinary strategy for evaluating the potential of plant-derived antimicrobial phenolic compounds for food preservation. A screening of the antimicrobial activity in vitro against 8 strains of foodborne pathogenic and spoilage microorganisms of a hundred pure molecules and about sixty plant extracts allowed to select the most active. Different mechanisms of action with respect to S. aureus could be demonstrated by flow cytometry coupled with the use of probes of the physiological state of the bacteria for some of the selected active compounds. For application to beef, the antibacterial activity of the most active phenolic compounds or plant extracts has been re-evaluated in more complex culture media mimicking their protein and fat content. The results of this screening and a microbiological monitoring of minced beef with 1% (m / m) of added extract made it possible to observe that the observed losses of antibacterial activity were in particular correlated with the interactions of the phenolic compounds with the proteins or fat. Incorporation of phenolic compounds or plant extracts into packaging materials in contact with food constituted was the second proposed route of implementation. Plastic films that retain antibacterial activity have thus been able to be prepared by melting

Tesis por compendio / [EN] The main goal of this Thesis was to determine the influence of the main processing stages involved in obtaining natural extracts with high antioxidant potential from byproducts originating in the olive oil industry. Firstly, the effect of freezing and/or the drying methods applied to olive oil byproducts on the polyphenol content and antioxidant capacity of the extracts subsequently obtained was addressed. For this purpose, two byproducts were considered: olive leaves and olive pomace. Secondly, the feasibility of intensifying the extraction of olive leaf polyphenols by means of a new technology, such as power ultrasound, was approached taking both compositional and kinetic issues into account. Thirdly, how the processing conditions (drying and extraction) influence the extract's stability was evaluated. Thus, on the one hand, extracts obtained from olive leaves were subjected to in vitro digestion or dehydrated and stored at different conditions. Finally, the possibility of obtaining a dried vegetable matrix (apple) rich in olive leaf phenolic compounds was explored by addressing the influence of apple pretreatments (blanching and freezing) and drying on the final retention of infused phenolics. The antioxidant potential of extracts and the retention of infused polyphenols in apple were evaluated by means of the total phenolic content and antioxidant capacity analysis, as well as the identification and quantification of the main olive leaf polyphenols by HPLC-DAD/MS-MS. Moreover, in apple samples, the polyphenol oxidase and peroxidase activity and microstructure were also analyzed. The experimental results highlighted that both drying and freezing methods significantly (p<0.05) influenced the concentration of the main polyphenols identified in the olive leaf extracts. Thus, drying at the highest temperature tested was the best processing condition in which to obtain extracts with high antioxidant capacity and phenolic content. Ultrasound application was found to be a relevant, non-thermal way of speeding-up the antioxidant extraction from olive leaves. Thus, by appropriately tuning-up the process variables, the ultrasonic assisted extraction shortened the extraction time from the 24 h needed in conventional extraction to 15 min, without modifying either the extract composition or the antioxidant potential. As far as extract stability is concerned, the processing conditions used for obtaining the olive leaf extracts did not have a meaningful influence on bioaccessibility. Regardless of the method used, stabilizing the extracts by means of dehydration only reduced both the antioxidant capacity and the total phenolic content by around 10 %. Moreover, storage conditions did not show a significant (p<0.05) effect on the antioxidant potential of the extracts for 28 days of storage. A stable dried product (apple), rich in natural phenolic compounds (from olive leaves or tea extracts), was obtained by combining drying-impregnation-drying steps. However, it should be considered that the role of fresh apple drying on the retention of infused olive leaf polyphenols was more important than the further drying of the impregnated apple. In overall terms, olive leaves can be considered a potential source of natural phenolic compounds. Notwithstanding this, the previous drying and freezing steps applied in the raw material processing are decisive factors in the obtaining of natural extracts with high antioxidant potential. Moreover, enhancing the extraction by applying power ultrasound was stated as a non-thermal way of shortening processing times. The stability of olive polyphenols during storage and in vitro digestion was closely related to the individual component considered. Finally, the exploitation of olive leaf extracts as a means of enriching solid foodstuffs requires the use of porous solid matrices free of oxidative enzymes. / [ES] El objetivo principal de esta Tesis fue determinar la influencia de las principales etapas de procesado implicadas en la obtención de extractos naturales con alto potencial antioxidante a partir de los subproductos originados en la industria del aceite de oliva. En primer lugar, se evaluó el efecto de los métodos de congelación y/o secado de la materia prima (hojas y orujo), sobre el contenido polifénolico y la capacidad antioxidante de los extractos. En segundo lugar, se abordó la intensificación de la extracción de polifenoles de hoja de olivo con ultrasonidos de potencia, teniendo en cuenta: composición y la cinética del proceso. A continuación, se estudió cómo las condiciones de procesado (secado y extracción) podían influir en la estabilidad de los extractos. Así, extractos de hojas de olivo fueron sometidos a digestión in vitro o deshidratados y almacenados a distintas condiciones. Por último, se exploró la posibilidad de obtener una matriz vegetal deshidratada (manzana) y rica en compuestos fenólicos de hoja de olivo. Para ello, se evaluó la influencia de los pretratamientos de la manzana (escaldado y congelación) y del secado en la retención final de los polifenoles impregnados. El potencial antioxidante se determinó a través del contenido total en compuestos fenólicos y la capacidad antioxidante y la identificación y cuantificación (HPLC-DAD/MS-MS) de los principales polifenoles. Además, en manzana, se midió la actividad enzimática de la polifenol oxidasa y peroxidasa y se analizó la microestructura. Los resultados manifestaron que el método de secado y el de congelación influyeron significativamente (p<0.05) en la concentración de los principales polifenoles en los extractos. Así, el secado a mayor temperatura resultó ser el mejor tratamiento para obtener extractos con alta capacidad antioxidante y alto contenido fenólico. La aplicación de ultrasonidos resultó ser una alternativa no térmica muy interesante para acelerar la extracción de antioxidantes de hojas de olivo. Con la combinación adecuada de las variables del proceso, la aplicación de ultrasonidos redujo el tiempo de extracción de 24 h necesarias en extracción convencional a 15 min, sin modificar la composición de los extractos y su potencial antioxidante. En cuanto a la estabilidad del extracto, las condiciones de procesado no tuvieron una influencia significativa en la bioaccesibilidad de los extractos. Independientemente del método utilizado, la estabilización de extractos por deshidratación sólo redujo la capacidad antioxidante y el contenido total en compuestos fenólicos en torno a un 10 %. Además, las condiciones de almacenamiento no mostraron ningún efecto significativo (p<0.05) sobre el potencial antioxidante durante los 28 días de almacenamiento. Combinando secado-impregnación-secado, fue posible desarrollar un producto deshidratado (manzana), estable y rico en compuestos fenólicos naturales (de hojas de olivo o extractos de té). No obstante, cabe destacar que el secado de la manzana fresca jugó un papel más importante en la retención de los polifenoles de hoja de olivo infundidos que el secado final de la manzana impregnada. En términos generales, las hojas de olivo pueden considerarse como una fuente potencial de compuestos fenólicos naturales. No obstante, el secado y la congelación durante el procesado de la materia prima son factores decisivos para la obtención de extractos naturales con alto potencial antioxidante. Además, la aplicación de ultrasonidos de potencia durante la extracción puede resultar una alternativa no térmica muy interesante de cara a acortar el tiempo de procesado. La estabilidad de los polifenoles de la hoja de olivo, durante el almacenamiento y la digestión in vitro, dependió claramente del compuesto individual considerado. Finalmente, el empleo del extracto de hoja de olivo como medio para enriquecer alimentos sólidos requiere del uso de matrices s / [CA] L'objectiu principal d'aquesta tesi va ser determinar la influència de les principals etapes de processament implicades en l'obtenció d'extractes naturals amb alt potencial antioxidant procedents de subproductes de la indústria de l'oli d'oliva. En primer lloc, es va estudiar l'efecte de la congelació i/o els mètodes d'assecatge aplicats a fulles d'olivera i pinyolada sobre el contingut fenòlic i la capacitat antioxidant dels extractes. En segon lloc, es va avaluar, tenint en compte la composició i la cinètica del procés, la intensificació de l'extracció de polifenols de fulla d'olivera amb ultrasons de potència. En tercer lloc, es va avaluar com les condicions de processament (assecatge i extracció) poden influir en l'estabilitat dels extractes. Així, extractes de fulles d'olivera van ser sotmesos a una digestió in vitro o deshidratats i emmagatzemats a distintes condicions. Finalment, es va explorar la obtenció d'una matriu vegetal deshidratada (poma) i rica en compostos fenòlics de fulla d'olivera considerant la influència del pretractament de la poma (escaldament i congelació) i de l'assecatge sobre la retenció final dels fenòlics introduïts en la poma. El potencial antioxidant es va avaluar determinant el contingut fenòlic total i la capacitat antioxidant, així com identificant i quantificant els principals polifenols (HPLC-DAD/MS-MS). A més, en poma l'activitat enzimàtica de la polifenoloxidasa i la peroxidasa i la microestructura. Els resultats experimentals van destacar que el mètode d'assecatge i el de congelació van influir significativament (p<0,05) en la concentració dels principals polifenols identificats en els extractes. L'assecatge a la temperatura més alta que es va provar va resultar la millor condició de processament per a obtenir extractes amb una alta capacitat antioxidant i un alt contingut fenòlic. L'aplicació d'ultrasons va ser una manera rellevant i no tèrmica d'accelerar l'extracció d'antioxidants de les fulles d'olivera. Així, amb la combinació adequada de les variables del procés, l'extracció assistida per ultrasons va escurçar el temps d'extracció, de les 24 h requerides en l'extracció convencional a 15 min, sense modificar la composició de l'extracte ni el potencial antioxidant. Quant a l'estabilitat de l'extracte, les condicions de processament utilitzades per a l'obtenció dels extractes de fulla d'olivera no van tenir una influència significativa en la bioaccessibilitat. Independentment del mètode utilitzat, l'estabilització dels extractes per mitjà de la deshidratació només va reduir la capacitat antioxidant i el contingut fenòlic total al voltant d'un 10 %. A més, les condicions d'emmagatzematge (temperatura i forma de l'extracte: líquid o pols) no van mostrar cap efecte significatiu (p<0,05) en el potencial antioxidant dels extractes durant els 28 dies d'emmagatzematge. Combinant etapes d'assecatge-impregnació-assecatge fou possible obtenir un producte assecat estable (poma) i ric en compostos fenòlics naturals (de fulles d'olivera o te). No obstant això, cal destacar que l'assecatge de la poma fresca va ser més important i determinant en la retenció dels polifenols de fulla d'olivera que no l'assecatge de la poma impregnada. En termes generals, les fulles d'olivera es poden considerar com una font potencial de compostos fenòlics naturals. No obstant això, l'aplicació d'assecatge i congelació durant el processament de la matèria primera són factors decisius per a l'obtenció d'extractes naturals amb un alt potencial antioxidant. A més, l'aplicació d'ultrasons de potència durant l'extracció resultà ser una forma no tèrmica de millorar el procés, tot reduint-ne el temps d'extracció. L'estabilitat dels polifenols d'olivera durant l'emmagatzematge i la digestió in vitro va dependre del compost individual considerat. Finalment, la utilització d'extractes de fulla d'olivera per a desenvolupar aliments sòlids enriquits requ / Ahmad-Qasem Mateo, MH. (2015). ASSESSMENT OF THE INFLUENCE OF PROCESSING CONDITIONS ON THE ANTIOXIDANT POTENTIAL OF EXTRACTS OBTAINED FROM OLIVE OIL INDUSTRY BYPRODUCTS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/53452 / Premios Extraordinarios de tesis doctorales / Compendio

Tesis por compendio / [ES] Toneladas de aceite de oliva son producidas cada año en el área mediterránea, generando aguas residuales con elevada carga orgánica (COD) y polifenoles (TPhs). Los TPhs son compuestos fitotóxicos, sin embargo, poseen una alta actividad antioxidante, siendo valiosos para su comercialización. La Tesis Doctoral pretende implementar la economía circular para el tratamiento de estas aguas residuales. Para ello, varias combinaciones de procesos fueron estudiados, para recuperar TPhs y reincorporar estas aguas en el proceso productivo. El agua estudiada corresponde a agua de lavado de aceite de oliva (OOWW, "olive oil washing wastewater"), obtenida a la salida de la centrifugación vertical (lavado del aceite), generada en la elaboración de aceite de oliva mediante centrifugación de dos fases. El estudio contempla la utilización de procesos de membrana, resinas de adsorción y tratamiento biológico. Primero se realizó un pretratamiento (flotación, sedimentación y filtración con cartucho) eliminando 89% de grasas y aceites y 40% de color, turbidez y sólidos en suspensión. Luego fue alimentada al proceso de Ultrafiltración (UF) para obtener un permeado rico en TPhs con baja COD. Diferentes membranas, condiciones operacionales (presión transmembranal (TMP) y velocidad tangencial (CFV)) y protocolos de limpieza fueron estudiados. Modelos matemáticos semi-empíricos, método de superficies de respuesta (RSM) y redes neuronales artificiales (ANN) fueron utilizados para predecir el comportamiento de la densidad de flujo de permeado y analizar el tipo de ensuciamiento predominante. La membrana UP005 a TMP de 2 bar y CFV de 2.5m/s fue seleccionada, con una densidad de flujo de permeado estable de 40L/h·m2, bajo rechazo de TPhs (8%) y alto rechazo de COD (61%). Los modelos matemáticos indicaron que más de un proceso de ensuciamiento contribuyeron al ensuciamiento de las membranas. El análisis estadístico ANOVA de RSM mostró que la CFV como la TMP afectan a la densidad de flujo de permeado. Mediante ANN fue posible predecir los datos experimentales de variación de densidad de flujo de permeado con el tiempo. La nanofiltración (NF) y la ósmosis directa (FO) se estudiaron para concentrar los TPhs presentes en el permeado de UF. En la NF se analizaron varias membranas bajo diferentes condiciones operacionales para obtener el mayor rechazo de TPhs. La membrana NF270 a CFV de 1m/s y TMP de 10 bar, logró una densidad de flujo de permeado estable de 74L/h·m2, rechazo de TPhs del 94% y rechazo de COD del 83%. Para el estudio del ensuciamiento de las membranas se utilizaron dos técnicas espectroscópicas, fluorescencia 2D y FTIR, obteniendo información sobre la adsorción de algunos compuestos sobre la superficie de las membranas, y evaluar la eficiencia del protocolo de limpieza. En la FO dos membranas fueron analizadas para la concentración de TPhs. También se estudió el uso de aguas residuales procedentes de la etapa de fermentación en la elaboración de aceitunas de mesa (FTOP) como disolución de arrastre debido a su alta salinidad. Con la membrana HFFO6 (caudal de 30 L/h) se logró la concentración de TPhs en un 79% y la dilución de la FTOP. Cuatro resinas de adsorción fueron estudiadas para recuperar los TPhs presentes en los concentrados de la FO y de la NF. Se estudiaron diferentes concentraciones de resina, tiempos de contacto y disolventes de desorción para la obtención de un concentrado puro, rico en TPhs. Los mejores resultados se obtuvieron con 40 g/L de resina MN200 y una disolución 50% etanol/agua como disolvente. Finalmente, las aguas resultantes (concentrado de FO y rechazos de NF y UF) fueron sometidas a tratamientos biológicos. Primero se realizaron estudios para evaluar la concentración inicial de los reactores biológicos. Mediante tratamiento biológico SBR se logró eliminar en gran medida la COD y los TPhs (rechazo de UF) presentes, logrando obtener efluentes con características aptas para ser utilizadas como agua de limpieza de maquinaria. / [CA] Tones d'oli d'oliva són produïdes cada any a l'àrea mediterrània, generant aigües residuals amb càrrega orgànica elevada (COD) i polifenols (TPhs). Els TPhs són compostos fitotòxics, no obstant això, tenen una alta activitat antioxidant, sent valuosos per a la seva comercialització. La Tesi Doctoral pretén implementar l¿economia circular per al tractament d¿aquestes aigües residuals. Per això, diverses combinacions de processos van ser estudiats, per recuperar TPhs i reincorporar aquestes aigües al procés productiu. L'aigua estudiada correspon a aigua de rentat d'oli d'oliva (OOWW, olive oil washing wastewater), obtinguda a la sortida de la centrifugació vertical (rentat de l'oli), generada en l'elaboració d'oli d'oliva mitjançant centrifugació de dues fases. L'estudi contempla la utilització de processos de membrana, resines d'adsorció i tractament biològic. Primer es va realitzar un pretractament (flotació, sedimentació i filtració amb cartutx) eliminant 89% de greixos i olis i 40% de color, terbolesa i sòlids en suspensió. Després va ser alimentada al procés d'Ultrafiltració (UF) per obtenir un permeat ric en TPhs amb baixa COD. Diferents membranes, condicions operacionals (pressió transmembranal (TMP) i velocitat tangencial (CFV)) i protocols de neteja van ser estudiats. Models matemàtics semi-empírics, mètode de superfícies de resposta (RSM) i xarxes neuronals artificials (ANN) van ser utilitzats per predir el comportament de la densitat de flux de permeat i analitzar el tipus d'embrutament predominant. La membrana UP005 a TMP de 2 bar i CFV de 2.5m/s va ser seleccionada, amb una densitat de flux de permeat estable de 40L/h·m2, baix rebuig de TPhs (8%) i alt rebuig de COD (61%) . Els models matemàtics van indicar que més d'un procés d'embrutament van contribuir a embrutar les membranes. L'anàlisi estadística ANOVA de RSM va mostrar que la CFV com la TMP afecten la densitat de flux de permeat. Mitjançant ANN va ser possible predir les dades experimentals de variació de densitat de flux de permeat amb el temps. La nanofiltració (NF) i l'osmosi directa (FO) es van estudiar per concentrar els TPhs presents al permeat d'UF. A la NF es van analitzar diverses membranes sota diferents condicions operacionals per obtenir el major rebuig de TPhs. La membrana NF270 a CFV de 1m/s i TMP de 10 bar, va aconseguir una densitat de flux de permeat estable de 74L/h·m2, rebuig de TPhs del 94% i rebuig de COD del 83%. Per estudiar l'embrutament de les membranes es van utilitzar dues tècniques espectroscòpiques, fluorescència 2D i FTIR, obtenint informació sobre l'adsorció d'alguns compostos sobre la superfície de les membranes, i avaluar l'eficiència del protocol de neteja. A la FO dues membranes van ser analitzades per a la concentració de TPhs. També es va estudiar l'ús d'aigües residuals procedents de l'etapa de fermentació en l'elaboració d'olives de taula (FTOP) com a dissolució d'arrossegament per la seva alta salinitat. Amb la membrana HFFO6 (cabal de 30 L/h) es va aconseguir la concentració de TPhs en un 79% i la dilució de la FTOP. Quatre resines d'adsorció van ser estudiades per recuperar els TPhs presents als concentrats de la FO i de la NF. Es van estudiar diferents concentracions de resina, temps de contacte i dissolvents de desorció per obtenir un concentrat pur, ric en TPhs. Els millors resultats es van obtenir amb 40 g/L de resina MN200 i una dissolució 50% etanol/aigua com a dissolvent. Finalment, les aigües resultants (concentrat de FO i rebutjos de NF i UF) van ser sotmeses a tractaments biològics. Primer es van fer estudis per avaluar la concentració inicial dels reactors biològics. Mitjançant tractament biològic SBR es va aconseguir eliminar en gran mesura la COD i els TPhs (rebuig d'UF) presents, aconseguint obtenir efluents amb característiques aptes per ser utilitzades com a aigua de neteja de maquinària. / [EN] Tons of olive oil are produced each year in the Mediterranean area, generating wastewater with a high organic load (COD) and polyphenols (TPhs). TPhs are phytotoxic compounds, however, they have a high antioxidant activity, being valuable for their commercialization. The Doctoral Thesis aims to implement the circular economy for the treatment of these wastewaters. For this, various combinations of processes were studied to recover TPhs and reincorporate these waters into the production process. The water studied corresponds to olive oil washing water (OOWW), obtained at the outlet of the vertical centrifugation (oil washing), generated in the production of olive oil by means of two-phase centrifugation. The study contemplates the use of membrane processes, adsorption resins and biological treatment. First, a pretreatment (flotation, sedimentation and cartridge filtration) was carried out, eliminating 89% of fats and oils and 40% of colour, turbidity and suspended solids. Then it was fed to the Ultrafiltration (UF) process to obtain a permeate rich in TPhs with low COD. Different membranes, operational conditions (transmembrane pressure (TMP) and cross low velocity (CFV)) and cleaning protocols were studied. Semi-empirical mathematical models, the response surface method (RSM) and artificial neural networks (ANN) were used to predict the behavior of the permeate flux density and to analyze the predominant type of fouling. The UP005 membrane at 2 bar TMP and 2.5m/s CFV was selected, with a stable permeate flux density of 40L/h·m2, low TPhs rejection (8%) and high COD rejection (61%). Mathematical models indicated that more than one fouling process contributed to the fouling of the membranes. Statistical analysis ANOVA of RSM showed that both CFV and TMP affect permeate flux density. Through ANN it was possible to predict the experimental data of permeate flux density variation over time. Nanofiltration (NF) and forward osmosis (FO) were studied to concentrate the TPhs present in the UF permeate. In the NF several membranes were analyzed under different operational conditions to obtain the highest rejection of TPhs. The NF270 membrane at CFV of 1m/s and TMP of 10 bar, achieved a stable permeate flux density of 74L/h·m2, TPhs rejection of 94% and COD rejection of 83%. To study the fouling of the membranes, two spectroscopic techniques were used, 2D fluorescence and FTIR, obtaining information on the adsorption of some compounds on the surface of the membranes, and evaluating the efficiency of the cleaning protocol. In the FO two membranes were analyzed for the concentration of TPhs. The use of wastewater from the fermentation stage in the production of table olives (FTOP) as a stripping solution due to its high salinity was also studied. With the HFFO6 membrane (flow rate of 30 L/h) the concentration of TPhs was achieved by 79% and the dilution of the FTOP. Four adsorption resins were studied to recover the TPhs present in the FO and NF concentrates. Different resin concentrations, contact times and desorption solvents were studied to obtain a pure concentrate, rich in TPhs. The best results were obtained with 40 g/L of MN200 resin and a 50% ethanol/water solution as solvent. Finally, the resulting waters (FO concentrate and NF and UF rejections) were subjected to biological treatments. First, studies were carried out to evaluate the initial concentration of the biological reactors. Using SBR biological treatment, it was possible to largely eliminate the COD and the TPhs (rejection of UF) present, managing to obtain effluents with suitable characteristics to be used as machinery cleaning water. / The authors acknowledge the financial support from the Spanish Ministry of Economy, Industry and Competitiveness through the project CTM2017-88645-R and The European Union through the Operational Program of the Social Fund (FSE) of the Comunitat Valenciana 2014-2020, ACIF-2018 and BEFPI-2021, and the Associate Laboratory for Green Chemistry-LAQV which is financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020). / Cifuentes Cabezas, MS. (2022). Recuperación de polifenoles de efluentes de almazara mediante procesos de membrana y tratamiento biológico de las corrientes de rechazo [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/191508 / Compendio

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: South African red wine is often acknowledged world wide as being full bodied and deep in colour. This is often the result of high temperatures that is experienced during the important growth stages of grapes especially post véraison. In the Robertson area in South Africa however, temperatures often exceeds the range for optimal anthocyanin development during these growth stages. The distinction between grapes being technologically ripe and being ripe on a phenolic level is also accepted as an important determining factor for the perfect time to pick grapes. In co-operative wineries such as Robertson Winery (RW) where grapes are delivered from a large area and different producers, it is difficult to individualise grape blocks when it comes to ripeness level in terms of sugar or phenolic ripeness. In most circumstances a generalised set of parameters for deeming grapes ripe or acceptable for delivery is the best substitute. The levels of these parameters are based on research literature that is available for the area as well as data collected through years of maintaining the vineyards of that area. The grape parameters that are currently being used by RW for ripeness and quality are pH, titratable acidity (TA) and sugar level. In recent years RW in conjunction with the Department of Viticulture and Oenology, Stellenbosch University, decided to investigate more parameters to determine the quality of grapes at the time of harvest. Most importantly for the grape growers this quality is connected to a price point and therefore compensation. Two important quality parameters of red wine are the red colour and mouth feel of wine. Anthocyanin and tannins are respectively connected to these two quality attributes and are both widely accepted as quality indicators. Wine with high anthocyanin and tannin content often originates from grapes with a high colour and phenolic profile. The existence of a correlation between grape and wine anthocyanin and tannin content is therefore the basis of attempting to use these parameters in the grape to predict end wine’s colour and phenolic quantity. Determination of anthocyanin and tannin content of grapes has already become part of some private owned wineries’ standard set of determinations. However, sample preparations, extractions and consumables needed are all factors that need to be reduced to make the measurement and therefore the use of these parameters more viable in a co-operative cellar laboratory, where large volumes of grapes are received during harvest. The first objective of this work was to determine the levels of anthocyanin and tannin in red grapes from different vineyard blocks from the producers of RW from three successive vintages. This would give insight as to what can be seen as a low and high anthocyanin and tannin content for grapes received at the cellar. For this purpose, blocks of the most important red wine cultivars for RW was selected and analysed for these compounds. The ranges and average levels of anthocyanin and tannin content were determined using measurement techniques that could be used by any winery. The average mono flavanol and total colour level of the grapes were found to be lower than those often reported in literature, with total grape flavanols being higher. However, a wide range of values for these compounds were found that correlated with those found in other studies. The possible reasons for differences in levels of occurrence of these compounds were discussed and mostly pertain to differences in cultivar, micro climatic and season. The second objective was to determine the correlation between levels of colour and phenolic compounds in grapes and their corresponding wines. Such correlations will form the foundation for the use of phenolic content to predict the colour and phenolic potential of the wine and possibly wine quality as well. When the grape and wine colour and phenolic data were correlated for all seasons and cultivars inclusive it was found that grape and wine colour showed better correlations than for instance total phenols and tannins. This was especially true for total colour pigments in red grapes, measured with HPLC, when correlated with certain spectrophotometric analysis of wine colour. Cultivar and season as well as the synergism between the two were further investigated for its role in affecting correlations. When these relationships were further differentiated by season and by cultivar the resulting correlations varied. This work contributed a great deal of information to support the use of grape colour and phenolic compounds for the prediction of end wine colour and phenolic composition. The third objective was to investigate near infrared spectroscopy (FT-NIR) as a viable option to rapidly measured anthocyanins, tannins and total phenolics in red grapes. If proven successfully, this could be employed by a large cellar such as RW. FT-NIR has been used with success on grape extracts and in this instance the focus was to establish a calibration on the grape homogenate itself. Preliminary results showed that FT-NIR could be applied for the use of determination of anthocyanin and tannin levels in red grapes originating from RW. The prediction of total phenols was not found to be as accurate, but this could also be due to the reference method that was used. This work brought some interesting, practical information not only of importance for RW, but all wineries that are concerned with improving the basis on which grape quality is determined. The use of aerial data mapping for indicating areas regarding important grape colour and phenolic parameters was used in this study and is a very visual way of showing the distribution of certain ripeness parameters over a large area. Correlations between the grape and wines of such a large amount of red grape blocks for a specific area have not also been reported in South Africa before. The use of FT-NIR to determine anthocyanins and tannin concentrations in grape homogenates is also novel for its use in South African wineries. This work may assist grape and wine producers as well as analysts on the phenolic and colour profile of grapes and wines from RW. / AFRIKAANSE OPSOMMING: Suid-Afrikaanse rooiwyn word wêreld-wyd geken aan ‘n dieprooi kleur en vol struktuur. Die grootste rede vir hierdie verskynsel is hoë temperature wat ervaar word tydens rypwording en veral na véraison. In die Robertson wynstreek is temperature egter tydens rypwording dikwels vêr bo dit was as optimaal vir antosianien ontwikkeling beskou word. Die gepaste tyd om druiwe te pluk word nie net gedryf deur die tegnologiese rypheidsvlak nie, maar ook deur fenoliese rypheid. In ‘n koöperatiewe kelder omgewing soos Robertson Wynkelder (RW) word ‘n hoë lading druiwe elke dag ontvant vanaf verskillende produsente oor ‘n breë streek. Dit maak dit moeilik om te bepaal watter druiwe werklik beide tegnologies en fenolies ryp is. Die beste manier om hiervoor te vergoed is om ‘n standaard te stel vir ‘n reeks voorafbepaalde parameters. Die vlakke van die gekose parameters is, word bepaal deur navorsinguitsette sowel as die geskiedkunde data wat ingesamel is vanaf elkeen van die bepaalde blokke. Die parameters wat tans in gebruik is by RW om oesdatum en kwaliteit by inname te bepaal is pH, titreerbare suur (TA) en suiker vlak. Die tekortkoming hier is dat kwaliteit van druiwe beswaarlik met slegs hierdie informasie kan bepaal word, maar dat dit die betaling van die produsent by aflewering wesenlik kan beïnvloed. Dit het RW genoop om in samewerking met die Departement van Wingerd en Wynkunde, Universiteit van Stellenbosch nog parameters te ondersoek wat hierdie rypheid- en kwaliteitsbepaling by inname sou kon versterk. Twee belangrike faktore wat kwaliteit van rooiwyn bepaal is die kleur en struktuur. Antosianiene en tanniene is onderskeidelik verantwoordelik vir hierdie kwaliteits eienskappe van wyn. Wyn wat bestempel word as hoog in kleur en tannien inhoud word dikwels verbind met druiwe wat hoog is in hierdie faktore. Die moontlike korrelasie tussen die antosianien en tannien inhoud van druiwe en die wyn wat daarvan berei word is dus die basis waarop die potensiële toepassing van hierdie parameters berus. Die bepaling van antosianien en tannien vlakke word reeds in sommige laboratoriums gedoen. Die monster voorbereidings tyd, ekstraksies, toerusting en verbruikbare items nodig om hierdie tipe analieses te doen is egter hoog. Die analiese van hierdie komponente is meer lewensvatbaar in groot laboratoriums (soos in ‘n koöperatiewe kelder) waar groter volume druiwe ingeneem word gedurende parstyd. Die eerste doelwit van hierdie studie was om te bepaal teen watter vlakke antosianiene en tanniene in druiwe voorkom, spesifiek van die Robertson area. Die het behels ‘n wye verskeidenheid van blokke, verspreid oor die hele streek wat oor 3 seisoene gemonitor is in terme van veral kleur en tanniene maar ook ander belangrike parameters. Die idee hier is om insig te kry rakende watter vlakke bestempel kan word as laag en hoog in terme van antosianien en tanniene vir die Robertson streek. Daarvoor is slegs die mees aangeplantste rooi kultivars gebruik. Die verspreiding en gemiddelde vlakke waarteen antosianien en tanniene voorkom was bepaal deur gebruik te maak van metodes wat as relatief algemeen in laboratoria gebruik word. Die gemiddelde mono-flavonoïed en totale kleur pigment inhoud van die druiwe was laer as van die vlakke wat in die literatuur beskikbaar is, met totale flavanole wat hoër was. Die wyer verspreiding van die waardes het egter beter gekorreleer met die waardes soos beskryf in die literatuur. Die moontlike redes vir die verskillende vlakke word in die studie bespreek en word waarskynlik bepaal deur verskille in kultivar, mikro-klimaat en seisoen. Die tweede doelwit was om te bepaal of daar ‘n korrelasie te vinde is tussen die kleur en tannien inhoud van die druiwe en ooreenstemmende wyne. Sulke tipe korrelasies sal die basis vorm om antosianien en tannien inhoud van wyn reeds in die druiwe fase te kan voorspel. Nadat die ingesamelde druif en wyn data as ‘n geheel beskou was, was dit sigbaar dat die wynkleur parameters beter korrelasies bied as meeste tannien en totale fenole. Dit was veral waar in die geval van totale kleur pigmente soos gemeet met die HPLC teenoor die wynkleur parameters gemeet met spektrofotometriese metodes. Verdere ondersoeke in terme van die impak wat die kultivar en seisoenale kan hê het tot variërende korrelasies gelei.. Hierdie werk het ‘n groot bydrae gelewer om voorspellings van wyn kleur en fenoliese inhoud reeds met sukses vanaf die druif te bepaal. Derdens het die werk fourier transformasie naby infrarooi skandering (FT-NIR) ondersoek as ‘n lewensvatbare metode vir die bepaling van antosianien, tannien en totale fenoliese inhoud van druiwe en wyn. FT-NIR word reeds oor ‘n wye reeks wyne en druiwe ekstraksiemonsters toegepas en die doelwit hier was om druiwe homogenaat as matriks te kalibreer. Voorlopige resultate het bevind dat antosianien en tannien vlakke in druiwe van RW gemeet kan word met die FT-NIR, maar dat die kalibrasie vir totale fenole nog verbeter kan word. Hierdie werk het ‘n wye reeks interessante en prakties bruikbare informasie na vore gebring wat van onskatbare belang is vir RW en ander kelders wat besorgd is oor die verbetering van algemene druifkwaliteit. Geografiese kaarte wat belangrike druifkleur en fenoliese parameters aandui is in hierdie studie gebruik en wys hoe data visueel voorgestel kan word om die geheelindruk van gekose parameters oor ‘n groot area te vergelyk. Korrelasies tussen druiwe en wyn van so ‘n groot hoeveelheid druiwe blokke is nog nooit voorheen in Suid-Afrika getoon nie. Dieselfde geld vir die gebruik van FT-NIR vir die meet van kleur en fenoliese parameters in druiwe homogenate. Hierdie werk kan druiwe- en wynproduseerders sowel as analiste assisteer in terme van die kleur en fenoliese profiel van druiwe en wyn van RW. / Robertson Winery with Mr Bowen Botha as well as THRIP for funding this project

Thesis (MScAgric)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Phenolic compounds are important quality indicators of a red wine, as they can contribute to the colour of a young red wine, colour stability during ageing as well as astringency, bitterness, body and overall mouthfeel properties. Wine composition is commonly influenced by winemaking and viticultural practices. In South Africa it often happens that vines are excessively vigorous, resulting in canopies that are too dense, which in turn could have a negative effect on the quantity and quality of the grapes produced. Viticultural practices such as judicious canopy management and irrigation are designed to control vine vigour and yield, thus improving fruit ripening and colour development. Artificial shading and water deficit have been reported to have an influence on the sensory properties of red wine as well as on the flavonoid composition. These effects are dependent on a number of factors, however, including the season, cultivar, light intensity, and the extent and timing of water deficit. There is limited research on the possible interactive effects of grapevine water deficits and canopy manipulation on grape and wine flavonoid composition in Shiraz, as well as the relationships between berry and wine composition. We thus investigated the effect of canopy reduction in combination with water deficit on the phenolic and colour composition of Shiraz grapes at different levels of ripeness, and in their corresponding wines after alcoholic and malolactic fermentation as well as after six months’ ageing. This study found that it is possible to improve the phenolic composition of grapes and wine by shoot removal, and some of the tendencies in the wines were also observed after the ageing period. If the shoot removal is not performed at a very early stage, sunburn damage can occur and this will result in berries with a lower mass and volume at harvest due to excessive exposure without the berry having adapted to the imposed conditions. Harvesting at different ripeness levels also affected the chemical and phenolic composition of the grapes and resulting wines. The water deficit effect on most phenolic parameters measured in the grapes and wine was not as prominent as that of the canopy manipulation treatment. This study improved our understanding of how an improvement in the canopy microclimate of Shiraz could be reflected in the phenolic composition of wines, along with a potentially important effect of harvesting date. On this basis it may be possible to attain a specific wine style. Harvesting at a ripe stage, for example, could result in the production of wines with higher colour density and astringency, while unripe grapes could result in wines with higher levels of perceivable fresh berry attributes. In particular, canopy reduction could increase the astringency and body of wines made from grapes subjected to water deficit. / AFRIKAANSE OPSOMMING: Fenoliese verbindings is belangrike kwaliteitsparameters van rooiwyn, aangesien dit kan bydra tot die kleur van ‘n rooiwyn, kleurstabiliteit tydens veroudering sowel as frankheid, bitterigheid en mondgevoel. ‘n Wyn se fenoliese samestelling word algemeen bepaal deur wynmaak- en wingerdkundige praktyke. In Suid-Afrika gebeur dit gereeld dat wingerde uitermatig groeikragtig is, wat lei tot te digte lower wat sodoende ‘n negatiewe effek op kwantiteit en kwaliteit van die druiwe wat geproduseer word, het. Wingerdkundige praktyke soos oordeelkundige lowerbestuur en besproeiing is ontwerp om wingerdstokke se groeikrag en opbrengs te beheer, en sodoende vrugrypwording en kleurontwikkeling te verbeter. Kunsmatige beskaduwing en waterstres is gerapporteer om ‘n invloed te hê op die sensoriese eienskappe van rooiwyn sowel as op die flavonoïedsamestelling. Hierdie effekte is egter afhanklik van ‘n verskeidenheid faktore, insluitende die seisoen, kultivar, ligintensiteit en die mate en tyd van waterstres toegepas. Daar is beperkte navorsing op die moontlike interaktiewe effekte van waterstres en lowermanipulasie op die druif en wyn flavonoïedsamestelling in Shiraz, sowel as die verhoudings tussen druif en wyn samestelling. Ons het dus die effekte van lowerbestuur in kombinasie met waterstres op die fenoliese en kleursamestelling van Shiraz druiwe by verskillende rypheidsvlakke ondersoek, asook in hul ooreenstemmende wyne na alkoholieseen appelmelksuurfermentasie sowel as na ses maande veroudering. Hierdie studie het gevind dat dit moontlik is om die fenoliese samestelling van druiwe en wyn deur lootverwydering te verbeter, en sommige van die tendense is ook waargeneem in die wyn na die verouderingsperiode. Indien lootverwydering nie toegepas word by ‘n baie vroeë stadium nie, kan sonbrand voorkom en dit kan lei tot korrels met ‘n laer massa en volume by oes as gevolg van oormatige blootstelling sonder dat die korrel aangepas het by die spesifieke kondisies. Oes by verskillende rypheidsvlakke affekteer ook die chemiese en fenoliese samestelling van die druiwe en ooreenstemmende wyne. Die waterstreseffek op meeste van die fenoliese parameters gemeet in druiwe en wyn was nie so prominent soos dié van die lowermanipulasie behandeling nie. Hierdie studie het ons begrip verbeter van hoe ‘n verbetering van die lower mikroklimaat van Shiraz gereflekteer kan word op die fenoliese samestelling van die wyn, saam met ‘n potensiële belangrike effek van oesdatum. Op grond van hierdie basis is dit dus moontlik om ‘n spesifieke wynstyl te verkry. Oes by ‘n ryp stadium, byvoorbeeld, kan die produksie van wyn met ‘n hoër kleurdigtheid en frankheid tot gevolg hê, terwyl onryp druiwe wyne met hoër vlakke van waarneembare vars bessiekenmerke tot gevolg kan hê. Verlaging van lowerdigtheid kan veral die frankheid en mondgevoel van wyne gemaak van druiwe blootgestel aan waterstres, verbeter.

L’un des défis majeurs dans le domaine des polymères est la substitution des molécules pétro-sourcées en vue de l’élaboration de monomères, polymères et d'additifs pour polymères. Le travail de cette thèse s’axe sur la valorisation de molécules bio-sourcées et plus particulièrement, du cardanol et de dérivés d'huiles végétales. Le champ d’application des polymères étant large, nous avons choisi de nous centrer sur trois grandes problématiques.Dans un premier temps, nous nous sommes intéressés à la plastification du PVC qui, actuellement, est majoritairement réalisée par des phtalates, famille d’esters pétro-sourcés vivement suspectés d’être des perturbateurs endocriniens. Des additifs de substitution ont ainsi été synthétisés par une chimie simple à partir du cardanol et d’esters gras. Des stabilités thermiques et des propriétés plastifiantes très satisfaisantes ont été obtenues. Enfin, des tests de toxicité et d’écotoxicité ont démontré l’absence d'impact perturbateur sur la sécrétion d'hormones sexuelles et la non toxicité vis-à-vis de l'environnement de ces plastifiants bio-sourcés.Dans un second temps, nous avons revisité la chimie des résines phénoplastes habituellement préparées à partir du phénol et du formaldéhyde, deux molécules classées CMR. Nous avons adapté cette chimie robuste à un phénol bio-sourcé, le cardanol, et à un aldéhyde bio-sourcé, le nonanal, pour obtenir des résines phénoliques souples. Cette propriété recherchée est le résultat d’une plastification interne des chaines lipidiques pendantes au sein du réseau polymère. Par cet exemple, l’intérêt des dérivés d’huiles végétales pour l’élaboration de matériaux souples a été démontré. Un compromis entre la souplesse des résines phénoliques et leurs résistances chimique et thermique a été atteint.Enfin, nous nous sommes tournés vers l’élaboration de polyuréthanes réticulés à partir d’un ester gras, d’un diester gras et d’un triglycéride porteurs de fonctions alpha-hydroxycétone (collaboration avec l’équipe CASYEN de l’ICBMS). L’apport de la fonction alpha-cétone sur la réactivité du polyol vis-à-vis du réactif isocyanate n’est que modeste par rapport à des dérivés présentant un groupement alcool isolé sur la chaine (huile de ricin) et alcool associé à une autre fonction alcool (triglycéride 1,2-diol). Néanmoins, la présence d’interactions intramoléculaires provenant des groupements cétone a permis d’exacerber la stabilité thermique des matériaux PU et d’élaborer des PU réticulés souples par plastification interne comme dans le cas des résines phénoliques.Cette thèse a ainsi démontré l’apport des phénols lipidiques tels que le cardanol et des chaines grasses dans l’amélioration de la stabilité thermique et de la souplesse au sein de matériaux polymères. / One of the major challenges in the field of polymers is the substitution of oil-based molecules for the development of monomers, polymers and polymer additives. The topic of this thesis is focused on the valorization of bio-sourced molecules and particularly, cardanol and vegetable oil derivatives. Since the scope of polymers is broad, we have chosen to focus on the following three major issues.At first, we were interested in the plasticization of PVC, which is most often carried out by phthalates, a family of oil-based esters strongly suspected to be endocrine disruptors. Alternative additives were thus synthesized by simple chemical reactions from cardanol and fatty esters. Good thermal stabilities and satisfactory plasticizing properties were obtained. Finally, toxicity and ecotoxicity tests have demonstrated the absence of a disruptive impact on the secretion of sex hormones and the non-toxicity towards the environment of these bio-sourced plasticizers.In a second step, we were interested in the chemistry of phenolic resins usually prepared from phenol and formaldehyde, two molecules classified as CMR substances. Thus, a bio-sourced phenol, cardanol, and a bio-sourced aldehyde, nonanal, were reacted to reach flexible phenolic resins. This peculiar property is the result of internal plasticization of the pendant lipid chains within the polymer network. By this example, the interest of vegetable oil derivatives for the production of flexible materials was demonstrated. Finally, a compromise between the flexibility of phenolic resins and their chemical and thermal resistances was reached.Finally, we turned to the development of crosslinked polyurethanes from a fatty ester, a fatty diester and a triglyceride exhibiting alpha-hydroxyketone functions (collaboration with the CASYEN team of the ICBMS). The contribution of the alpha-ketone function on the reactivity of the related to the isocyanate reagent is only modest compared to isolated alcohol type derivatives (castor oil) and alcohol associated with another alcohol function ( triglyceride 1,2-diol). Nevertheless, the presence of intramolecular interactions from ketone groups made possible to enhance the thermal stability of the PU materials and to develop flexible crosslinked PUs by internal plasticization, as in the case of phenolic resins.This thesis brings out the advantages provided by the use of lipid phenols such as cardanol and fatty chains for the improvement of thermal stability and flexibility of polymer materials.

A própolis é uma substância resinosa coletada pelas abelhas de diversas partes das plantas, como brotos, botões florais e exudados resinosos, conhecida por do ácido cinâmico e ácido benzócio, foram ainda encontrados o ácido pimárico, várias atividades biológicas como antimicrobiana, anti-inflamatória, antiproliferativa e antioxidante. Sua composição química depende de vários fatores, como a localização geográfica, vegetação e clima. A própolis brasileira com certificação de produto orgânico, proveniente do sul do Brasil, foi coletada e avaliada em diferentes estações do ano. Essa própolis é produzida em florestas nativas e áreas de reflorestamento, locais livres de contaminação por insumos agrícolas, metais pesados e poluição industrial. O objetivo deste trabalho foi avaliar a composição química e atividade antioxidante, considerando a variação sazonal das estações de verão, outono e primavera. Foram coletadas ao todo 78 amostras provenientes de 14 apiários distintos. O teor de compostos fenólicos totais e flavonoides foram feitos por métodos colorimétricos, a atividade antioxidante foi avaliada pelos métodos de sequestro dos radicais livres DPPH&bull;, ABTS+, sendo a capacidade antioxidante contra os radicais peroxila, determinado pelo método ORAC. O perfil químico do extrato de etanólico da própolis (EEPO) foi avaliado por cromatografia de camada delgada em fase reversa (CCDAE-FR), varredura no ultravioleta-visível (UV-vis) e cromatografia gasosa acoplada com espectrometria de massas (CGEM). A composição de voláteis foi analisada por CG-EM. Os teores de flavonoides variaram de não detectado até 4,76 mg.g-1 e de 6,80 a 72,55 mg.g-1 para fenólicos totais. Em relação à atividade antioxidante, a variação encontrada foi de 1,01 a 384,60 mg Trolox.g-1 para ABTS+, de 4,50 a 148,10 &micro;mol Trolox.g-1 para DPPH&bull; e de 0,20 a 1,25 &micro;mol Trolox.g-1 de amostra para o ORAC. Em relação às estações, o verão apresentou maior teor de flavonoides (p=6%) e o outono, maior teor de DPPH&bull; (p=7%). Com base no perfil químico pela técnica de CCDAE, foi possível classificar as 78 amostras em sete variantes distintas. Dentre os compostos presentes e derivados dos ácidos cinâmico e benzóico, analisados pela técnica CG/MS, identificou-se os compostos ácido pimárico, norolean-12 ene, alfa bisabolol e metil comate A. Também foram identificados oito compostos voláteis em grande quantidade como &alpha;-pineno (54,77%), &beta;- pineno (14,83%), &alpha;-limoneno (3,78%), &beta;- mirceno (9,29%), ?-candineno (2,11%), &gamma; -muroleno (1,86%), &beta;-felandreno (4,79%) e &alpha;-selineno (8,40%). Uma correlação estatística foi encontrada entre o teor de fenólicos totais e o método DPPH&bull;, p=0,78, diferentemente do teor de flavonoides que não apresentou correlação com a atividade antioxidante. Os resultados obtidos demonstraram que a própolis orgânica possui atividade antioxidante, embora apresente baixos teores de flavonoides. Não existe correlação entre os flavonoides e atividade antioxidante. Os compostos fenólicos e a atividade antioxidante foram influenciados pela sazonalidade, sendo o outono, a estação que apresentou teores maiores de fenólicos e atividade antioxidante. / Propolis is a resinous substance collected from plant buds, flowers, and exudates by Apis mellifera bees widely known for its biological activities such as antiviral, antimicrobial, anti-inflammatory, antiproliferative and antioxidant activities. Its chemical composition depends on many factors as geographic location, vegetation, and climate. A certified Brazilian propolis, originated from South Brazil, was collected and evaluated in different seasons. This kind of propolis is produced in native forest and in reforestation areas, where contamination derived from agricultural inputs, heavy metals, and factory fumes is found. Hence, the aim of this work was to evaluate the chemical composition and the antioxidant activity during seasonal variation in summer, autumn and spring. Seventy-eight samples were collected from 14 different apiaries. The phenolic compound content and flavonoids were performed by colorimetric methods. The antioxidant activity was evaluated by free radical scavenging methods such as DPPH&bull; and ABTS+. The antioxidant capacity against peroxil radicals was assessed by ORAC method. The chemical profiles of the organic propolis ethanolic extracts were evaluated by reversed-phase thin-layer chromatography (RP-TLC), ultraviolet (UV) scanning, and gas chromatography-mass spectrometry (GC-MS). Flavonoid content varied from non - detected to 4.76 mg. g-1 and 6.80 to 72.55 mg.g-1 for phenolics. The antioxidant activity varied from 1.01 to 384.60 mg Trolox.g-1 for ABTS+ and 4.50 to 148.10 &micro;mol Trolox.g-1 for DPPH. Considering the seasonal variation, summer presented the highest compound content for flavonoids (p=6%), meanwhile autumn presented the highest compound content for DPPH&bull; (p=7%). Thus, considering the chemical profile presented by RP-TLC, seven different variances of propolis were classified. Compounds such as pimaric acid, norolean-12-ene, alpha bisabolol, and methyl commate A were found by GC-MS technique on these seven variances. Eight volatile compounds were also identified as follow: &alpha;-pinene (54,77%), &beta;- pinene (14,83%), &alpha;-limonene (3,78%), &beta;-myrcene (9,29%), .-candinene (2,11%), &gamma; - muurolene (1,86%), &beta;-phellandrene (4,79%), and &alpha;-selinene (8,40%). In conclusion, the results demonstrated that autumn showed higher antioxidant activity by DPPH&bull; method than those produced in other seasons. A statistical correlation was found between phenolic compound and DPPH&bull;, p=0.78, differing from the flavonoid content which did not demonstrate a correlation with antioxidant activity. The results obtained showed that organic propolis presents antioxidant activity, although its flavonoid content is extremely low. On extent, there was no correlation between flavonoid content and antioxidant activity. Moreover, the seasonal variation showed its influence on phenolic compounds as well as on antioxidant activity, in which autumn presented the highest phenolic content and antioxidant activity.

INTRODUÇÃO: A erva-mate (Ilex paraguarienis), uma planta nativa e consumida em grande parte da América do Sul, apresenta diversos compostos bioativos que já demonstraram importante atividade antioxidante in vitro e in vivo. O chá mate é um produto desta planta cujas propriedades antioxidantes ainda não foram avaliadas em ensaios com humanos. OBJETIVO: Este projeto visa avaliar o potencial antioxidante do chá mate in vivo e ex vivo sobre o plasma e LDL de humanos após a ingestão de chá-mate. MÉTODOS: Indivíduos em jejum (n=20) tiveram seu sangue coletado em três momentos: antes, após uma hora e depois de 1 semana (7 dias) da ingestão diária de chá-mate. O plasma e a LDL obtidos nos três momentos foram submetidos à oxidação por três mecanismos diferentes [Cobre (Cu+2), lipoxigenase e peroxinitrito (SIN-1)] e em seguida foram medidos os produtos de peroxidação lipídica formados: a concentração de TBARs (substâncias reativas ao ácido tiobarbitúrico) e a formação de dienos conjugados empregando-se métodos espectrofotométricos. Também foram determinados o perfil antioxidante total do plasma (TAS), avaliação da lipoperoxidação plasmática basal (TBARs), avaliação da fragmentação da Apolipoproteína B após oxidação da LDL, por eletroforese em gel com SDS-PAGE e os níveis de expressão, por meio de análise de PCR real time, de alguns genes relacionados à produção de enzimas antioxidantes. Teste t de Student pareado foi utilizado para verificar se houve diferença estatisticamente significante entre os resultados das diversas análises antes e após o consumo do chá. RESULTADOS: Os resultados obtidos pela maioria dos ensaios realizados demonstraram que o consumo de chá mate aumentou a resistência à oxidação, a capacidade antioxidante plasmática e a expressão de genes relacionados à produção de enzimas antioxidantes. CONCLUSÃO: Esses resultados sugerem que o consumo de chá mate por período curto pode atuar como antioxidante por múltiplos mecanismos e portanto pode contribuir para diminuição do risco de desenvolvimento de doenças crônicas relacionadas a processos oxidativo. / Yerba Mate (Ilex paraguariensis) is a native and widely consumed South American plant. It contains high concentrations of bioactive compounds that respond for its high antioxidant activity in vitro and in vivo. This activity has not been demonstrated yet in humans for the mate tea, a product derived from Yerba Mate. OBJECTIVE: The aim of this study was to evaluate the antioxidant activity of maté tea in vivo and ex vivo on plasma and LDL human after ingestion of mate tea infusion. METHODS: Fasting peripheral venous blood samples of twenty healthy women (n=20) were taken in three different times: before drinking the tea, one hour later and after one week of daily consumption (7 days) of mate tea. The plasma and isolated LDL were oxidated with 3 different systems [copper (CuSO4), lipoxygenase and peroxynitrite (SIN-1)]. Next, the peroxidation products evaluated were: concentration of malonaldeyde (TBA) and conjugated dienes (lag time), using spectrophotometric methods. We also measured the plasma total antioxidant status (TAS), serum levels of malondialdehyde (MDA) as thiobarbituric substances (TBARS), fragmentation of apo B using SDS-PAGE and the level of antioxidant enzyme gene expression by PCR real time. Paired t student test was used to analyze the results before and after ingestion of mate tea. RESULTS: The results obtained by most of the tests showed that mate tea ingestion increased the plasma and LDL resistance by ex vivo oxidation, the plasma antioxidant capacity and the level of antioxidant enzyme gene expression. CONCLUSION: This study suggests that regular consumption of mate tea can act as an antioxidant by multiple mechanisms and thus may contribute decrease the risk of developing chronic diseases related to oxidative processes.