Functional polymer foams are considered as a promising field which could potentially produce foams with added value. Specifically, functionally graded foams are materials which are expected to provide better mechanical properties while preserving low density in comparison with regular foams. In this thesis, a preparation process of such foams is designed, examination of prepared structure and comparison of mechanical properties with regular foams is performed. The obtained results are discussed and further research in this field is proposed.

Die Adsorption von Additiven an den Oberflächen eines Kristallisates wird als eine hauptsächliche Ursache für die Beeinflussung von Kristallwachstum und Morphologie angesehen und spielt bei vielen Kristallisationsprozessen eine entscheidende Rolle. Gerade für die Calciumsulfate, die im Millionen-Tonnen-Maßstab jährlich in Deutschland verarbeitet werden, stellt der Additiv-Einsatz einen Hauptkostenfaktor dar, während gleichzeitig die Additivwirkung mechanistisch nicht ausreichend gut verstanden und damit derzeit nicht vorhersagbar ist. Zur Erlangung eines besseren Verständnisses wurden mit Hilfe von molekulardynamischen Computersimulationen die Prozesse in den Grenzflächen zwischen festen Calciumsulfaten und wässriger Additivlösung auf atomarer Ebene analysiert. Wesentlicher Untersuchungsschwerpunkt war dabei die Rolle des polaren Lösungsmittels Wasser auf die Wechselwirkung zwischen verschiedenen ionischen Additivspezies und den Salzkristallen.:1. Einleitung und Zielsetzung 1 2. Literatur 6 2.1. Kristallstrukturen der Calciumsulfate 7 2.2. Kristallmorphologie und relevante Kristallflächen 10 2.2.1. Kristallwachstum und Morphologie der Calciumsulfate 10 2.2.2. Theoretische Methoden zur Morphologievorhersage 13 2.2.3. Morphologievorhersage für die Calciumsulfate 18 2.3. Struktur von Mineral-Wasser-Grenzflächen 20 2.3.1. Experimentelle Untersuchungen 20 2.3.2. Simulationen 25 2.4. Morphologiebeeinflussung der Calciumsulfate durch Additive 26 2.4.1. Additive für Calciumsulfate und deren Wirkungsweise 26 2.4.2. Beeinflussung der Gipsmorphologie durch Zitronensäure und Aminosäuren 28 2.5. Stand der Technik von Adsorptionssimulationen 31 2.5.1. Methodenüberblick 31 2.5.2. Molekulardynamische Adsorptionssimulationen 33 2.5.3. Modellierungen und Simulationen der Calciumsulfat-Additiv- Wechselwirkung 44 3. Methodik 47 3.1. Simulationsbasis 49 3.1.1. Randbedingungen und Annahmen 49 3.1.2. Simulationsmethoden und -parameter 51 3.1.3. Kraftfeld 55 3.1.4. Erstellen von Simulationsboxen 60 3.2. Simulationen zur Morphologievorhersage 65 3.2.1. Durchgeführte Simulationen 66 iiiInhaltsverzeichnis 3.2.2. Berechnung der Morphologie im Vakuum 68 3.2.3. Berechnung der Morphologie in Lösung 69 3.2.4. Zusammenfassung 72 3.3. Simulationen der CaSO 4 -Wasser-Grenzfläche 74 3.3.1. Durchgeführte Simulationen 74 3.3.2. Charakterisierung der Oberflächenstabilität 75 3.3.3. Strukturelle Charakterisierung der Hydratationsschichten 77 3.3.4. Kinetische Charakterisierung der Hydratationsschichten 82 3.3.5. Thermodynamische Charakterisierung der Hydratations- schichten 83 3.3.6. Zusammenfassung 87 3.4. Simulation der Adsorption 89 3.4.1. Durchgeführte Simulationen 89 3.4.2. Berechnung der Adsorptionsenergie 103 3.4.3. Berechnung der Freien Adsorptionsenergie 106 3.4.4. Zusammenfassung 112 4. Ergebnisse und Diskussion 114 4.1. Morphologievorhersage und Flächenauswahl 115 4.1.1. Die Morphologie im Vakuum 115 4.1.2. Die Morphologie in Lösung 123 4.1.3. Flächenauswahl 126 4.2. Die Mineral-Wasser-Grenzfläche 127 4.2.1. Oberflächenstabilität 127 4.2.2. Strukturelle Charakterisierung der Hydratationsschichten 133 4.2.3. Kinetische Charakterisierung der Hydratationsschichten 153 4.2.4. Thermodynamische Charakterisierung der Hydratations- schichten 162 4.2.5. Einfluss der Simulationsmethodik 166 4.3. Die Adsorption 167 4.3.1. Einfluss des Lösungsmittels 167 4.3.2. Einfluss des Additivs 176 4.3.3. Einfluss der Fläche 186 4.3.4. Einfluss der Simulationsmethodik 201 5. Zusammenfassung und Ausblick 211 ivInhaltsverzeichnis Abkürzungsverzeichnis V-1 Literaturverzeichnis V-6 Abbildungsverzeichnis V-34 Tabellenverzeichnis V-38 A. Methoden A-1 A.1. Erstellen von Simulationsboxen mit Kristallschichten A-2 A.1.1. Randbedingungen A-2 A.1.2. Erstellen der Elementarzelle A-3 A.1.3. Erstellen der Oberflächenelementarzelle A-3 A.2. Voruntersuchungen zur Adsorption A-8 A.2.1. Ausgangssituation A-8 A.2.2. Finden energetisch günstiger Konformationen A-11 A.2.3. Berechnung der Freien Adsorptionsenergie A-13 A.2.4. Berechnung der Adsorptionsenergie A-23 A.3. Clusteranalyse A-24 B. Tabellen B-1 C. Abbildungen C-1

Tesis por compendio / [ES] Esta memoria de tesis presenta una contribución al estudio de la funcionalización de sustratos textiles mediante la encapsulación de diferentes compuestos empleando la técnica del electrohilado. La variabilidad de la electrohilatura, tanto a nivel del equipo empleado como del propio proceso de electrohilado, permite la posibilidad de obtener morfologías y composiciones de nanofibras completamente distintas. En este trabajo se han abordado dos técnicas de preparación de la solución polimérica a emplear durante el proceso, los métodos de emulsión y dispersión. Ambas técnicas han posibilitado la adición de varios compuestos que han aportados nuevas características a nanofibras de PVA electrohiladas. Tras analizar los resultados obtenidos de las nanofibras extruidas a partir de la solución por emulsión, se ha demostrado la capacidad de encapsular aceites esenciales, tomillo y salvia, mediante electrohilatura. La caracterización realizada a los velos nanofibrosos demuestran la aparición de microcápsulas a lo largo de la sección longitudinal de las fibras debido a la encapsulación del aceite en su interior. Por otro lado, el método de dispersión ha sido evaluado mediante la adición de cúrcuma, compuesto no soluble en agua, a una solución de PVA. Los datos resultantes de las caracterizaciones han evidenciado la capacidad de la cúrcuma de actuar como sensor halocrómico aún estando encapsulada en el interior de las nanofibras electrohiladas. Al mismo tiempo, se ha examinado si esta capacidad halocrómica se mantiene cuando las nanofibras de PVA, que inicialmente son solubles en agua, se someten a un proceso de reticulación con ácido cítrico para su insolubilización. Los resultados han demostrado la continuidad del halocromismo, aunque difiere en la tonalidad del color resultante. Finalmente, se concluye con una comparativa por adición de materia colorante mediante los dos métodos explicados a una solución polimérica. Los velos nanofibrosos fabricados a partir de la solución dispersada presentaban una notable coloración en su superficie, mientras que las nanofibras producidas a partir de la solución por emulsión no presentaban color, lo cual vuelve a justificar la encapsulación del aceite coloreado en el interior de la nanofibra. / [CA] Aquesta memòria de tesi presenta una contribució a l'estudi de la funcionalització de substrats tèxtils mitjançant l'encapsulació de diferents compostos emprant la tècnica de l'electrofilat. La variabilitat de l'electrofilatura, tant a nivell de l'equip emprat com del procés d'electrofilat propi, permet la possibilitat d'obtenir morfologies i composicions de nanofibres completament diferents. En aquest treball s'han abordat dues tècniques de preparació de la solució polimèrica a emprar durant el procés, els mètodes d'emulsió i de dispersió. Ambdues tècniques han possibilitat l'addició de diversos compostos que han aportat noves característiques a nanofibres de PVA electrofilades. Després d'analitzar els resultats obtinguts de les nanofibres extruïdes a partir de la solució per emulsió, s'ha demostrat la capacitat d'encapsular olis essencials, farigola i sàlvia, mitjançant electrofil·latura. La caracterització realitzada a les estores nanofibroses demostren l'aparició de microcàpsules al llarg de la secció longitudinal de les fibres a causa de l'encapsulació de l'oli al seu interior. D'altra banda, el mètode de dispersió s'ha avaluat mitjançant l'addició de cúrcuma, compost no soluble en aigua, a una solució de PVA. Les dades resultants de les caracteritzacions han evidenciat la capacitat de la cúrcuma d'actuar com a sensor halocròmic encara estant encapsulada a l'interior de les nanofibres electrofilades. Alhora, s'ha examinat si aquesta capacitat halocròmica es manté quan les nanofibres de PVA, que inicialment són solubles en aigua, se sotmeten a un procés de reticulació amb àcid cítric per a la seua insolubilització. Els resultats han demostrat la continuïtat de l'halocromisme encara que difereix en la tonalitat del color resultant. Finalment, es conclou amb una comparativa per addició de matèria colorant mitjançant els dos mètodes explicats a una solució polimèrica. Els vels nanofibrosos fabricats a partir de la solució dispersada presentaven una notable coloració a la superfície, mentre que les nanofibres produïdes a partir de la solució per emulsió no presentaven color, la qual cosa torna a justificar l'encapsulació de l'oli acolorit a l'interior de la nanofibra. / [EN] This thesis report presents a contribution to the study of the functionalisation of textile substrates through the encapsulation of different compounds using the electrospinning technique. The variability of electrospinning, both at the level of the equipment used and of the electrospinning process itself, allows the possibility of obtaining completely different morphologies and compositions of nanofibres. In this work, two techniques for the preparation of the polymer solution to be used during the process have been addressed, the emulsion and dispersion methods. Both techniques have allowed the addition of several compounds that have provided new properties to electrospun PVA nanofibres. After analysing the results obtained from the nanofibres extruded from the emulsion solution, the ability to encapsulate essential oils, thyme and sage, by electrospinning was demonstrated. The characterisation of the nanofibrous mats shows the appearance of microcapsules along the longitudinal section of the fibres, due to the encapsulation of the oil inside them. On the other hand, the dispersion method was evaluated by adding turmeric, a non-water soluble compound, to a PVA solution. The data obtained from the characterisations have showed the ability of turmeric to act as a halochromic sensor even when encapsulated in the electrospun nanofibres. At the same time, it was investigaed whether this halochromic capacity is maintained when the PVA nanofibres, which are initially soluble in water, undergo a cross-linking process with citric acid to insolubilise them. The results have shown the continuity of the halochromism, although the resulting shade is different. Finally, we compare the addition of dyes to a polymer solution using the two methods described above. The nanofibrous veils produced from the dispersed solution showed a noticeable colouration on their surface, whereas the nanofibres produced from the emulsion solution were colourless, which again justifies the encapsulation of the coloured oil inside the nanofibre. / Mínguez García, D. (2024). Funcionalización de textiles mediante encapsulación por electrohilatura [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/202719 / Compendio

Exogenously supplied organoselenium compounds, capable of propagating a selenium redox cycle, were shown to supplement natural cellular defenses against oxidants generated during biological activity. Phenylaminoalkyl selenides were developed in our laboratory as novel substrate analogs for the enzyme dopamine beta-monooxygenase. Recently, phenylaminoalkyl selenides were found to protect plasmid DNA and Molecular beacons from oxoperoxynitrate – mediated damage by scavenging this oxidant and forming the corresponding selenoxides as the sole selenium – containing products. Rate constants were determined for the reactions of the phenylaminoalkyl selenoxides with GSH at physiological pH and 25 degrees C. The kinetic data obtained in current and previous research was subsequently used in a MatLab simulation, which showed the feasibility of selenium redox cycling by GSH in the presence of a cellular oxidant, oxoperoxynitrate. Loblolly pine (LP, Pinus taeda) is the primary commercial species in southern forests covering 11.7 million hectares. Somatic embryogenesis (SE) is an effective technique to implement production of high value genotypes of LP. SE is a multi-step process, which includes initiation of somatic embryo (SME) growth from tree tissue, maintenance and multiplication of early stage SMEs and the maturation / germination phase. In this work, we isolated a substance from stage 2 or 3 LP female gametophyte (FG) tissue that stimulates early stage SME growth, and characterized this substance as citric acid on the basis of 1H NMR and mass spectrometry. We then demonstrated that topical application of citric acid to SMEs stimulates embryo colony growth at p = 0.05 for 3 of the 5 genotypes tested. Phenylketonuria (PKU) is an autosomal recessive disorder caused by an impaired conversion of L-phenylalanine (L-Phe) to L-tyrosine (L-Tyr). A novel assay based on enzymatic - colorimetric methodology (ECA) was developed in order to detect elevated concentrations of L-Phe in undeproteinized plasma of PKU patients via continuous spectrophotometric detection. We report here that L-Phe concentrations in undeproteinized plasma measured using our ECA were comparable to those determined on an amino acid analyzer based on Pearson correlation coefficients and a Bland and Altman comparison.

[EN] Persimmon (Diospyros kaki L.) 'Rojo Brillante' is an astringent variety characterised by good growing conditions, excellent colour, size, sensory characteristics and good nutritional properties. In the last decade, its production has grown substantially in Spain given the application of high levels of CO2 to remove astringency while firmness is preserved. This technology has also increased its potential as a fresh-cut commodity. However, physical damage during processing result in degradation of the colour and firmness of the product and a higher susceptibility to microbial spoilage that significantly reduces the fruit's shelf life. The objective of the present thesis was to develop optimum procedures for processing and marketing 'Rojo Brillante' persimmon into a fresh-cut product with the maximum shelf life and best physicochemical, nutritional, sensory and microbiological quality. Firstly, the objective was to evaluate the effect of the maturity stage (MS) at harvest, storage time at 15 ºC before processing, and the application of different antioxidant treatments on enzymatic browning, sensory and nutritional quality of fresh-cut 'Rojo Brillante' persimmon during storage at 5 ºC. Concentrations of 10 g L-1 ascorbic acid (AA) or 10 g L-1 citric acid (CA) controlled tissue browning and maintained the visual quality of fresh-cut persimmon above the limit of marketability for 6-8 storage days at 5 ºC, depending on the MS. However, these acidic solutions reduced fruit firmness as compared to control samples. Further studies showed that the combination of these antioxidants with 10 g L-1 CaCl2 maintained firmness of the persimmon slices within the same range as the control samples. In another work, the application of 1-methylcyclopropene (1-MCP) allowed to process fruits after 45 days of storage at 1 ºC with commercial firmness and the antioxidant solution (10 g L-1 CA + 10 g L-1 CaCl2) extended the limit of marketability up to 9 days of storage at 5 ºC. Different controlled atmosphere conditions in combination with AA or CA dips were also evaluated as a first step to select optimum O2 and CO2 concentrations for modified atmosphere packaging (MAP) of fresh-cut 'Rojo Brillante' persimmons. Overall, the combination of antioxidant dips and a controlled atmosphere composed of 5 kPa O2 (balance N2) was proved to be the most effective combination to control enzymatic browning. This atmosphere maintained the visual quality of persimmon slices within the limit of marketability during 7- 9 days at 5 ºC. On the contrary, high CO2 concentrations (10 or 20 kPa) induced darkening in some tissue areas, associated with a flesh disorder known as 'internal flesh browning'. Later studies confirmed the beneficial effect of an active MAP in 5 kPa O2 compared to passive MAP to improve the visual quality of fresh-cut 'Rojo Brillante' persimmon, showing a synergic effect with the antioxidant dip (10 g L-1 CA + 10 g L-1 CaCl2). Antioxidant edible coatings were prepared from whey protein isolate (WPI), soy protein isolate (SPI), hydroxylpropyl methylcellulose (HPMC) and apple pectin as the polymeric matrix. All edible coatings were amended with the antioxidant combination selected (10 g L-1 CA + 10 g L-1 CaCl2). All the edible coatings tested proved effective to control enzymatic browning of persimmon slices. However, the samples treated with the HPMC- and pectin- based coatings were scored with a better visual quality that the rest of the treatments. In general, free radical scavenging activity and total carotenoid content increased in late-season persimmons; whereas, processing (cutting and storage at 5 ºC), antioxidant dips, controlled atmosphere storage or edible coatings had no clear effect on nutritional quality (vitamin C, free radical scavenging activity, total phenolic content, and carotenoids) of fresh-cut persimmons. / [ES] El caqui persimmon (Diospyros kaki L.) 'Rojo Brillante' es un cultivar astringente que presenta unas propiedades organolépticas y nutricionales excelentes. En la última década, su cultivo en el área mediterránea de España se ha incrementado de manera exponencial con el desarrollo de la tecnología que permite eliminar la astringencia, manteniendo la firmeza del mismo. Esta nueva forma de presentación, aporta numerosas ventajas, entre la que se incluye la posibilidad de ser comercializado como fruta fresca cortada. Sin embargo, el éxito comercial del producto está limitado por el pardeamiento enzimático, la pérdida de firmeza y al crecimiento microbiano. En este contexto, el objetivo de la Tesis ha sido el desarrollo de caqui 'Rojo Brillante' fresco cortado mediante un enfoque que integra el estudio de las características del producto en el momento del procesado y de distintas tecnologías que mantengan la calidad físico-química, sensorial, nutricional y microbiológica del producto durante un periodo que permita su comercialización. En primer lugar, se evaluó el efecto del estado de madurez (MS) en el momento de recolección, el tiempo de almacenamiento a 15 ºC antes del procesado y la aplicación de diferentes antioxidantes en el pardeamiento enzimático y la calidad sensorial y nutricional del caqui 'Rojo Brillante' cortado y almacenado a 5 ºC. La aplicación de 10 g L-1 de ácido ascórbico (AA) ó 10 g L-1 ácido cítrico (CA) controló el pardeamiento enzimático y mantuvo la calidad visual del caqui por encima del límite de comercialización entre 6 y 8 días de almacenamiento a 5 ºC, dependiendo del MS. Sin embrago, la aplicación de estos antioxidantes redujo de manera significativa la firmeza del fruto respecto al control. La combinación de estos antioxidantes con 10 g L-1 de CaCl2 permitió mantener la firmeza en el mismo rango que las muestras control. En un trabajo posterior, la aplicación de 1-metilciclopropeno (1-MCP) permitió procesar caqui almacenado 45 días a 1 ºC con una buena firmeza comercial y el tratamiento antioxidante (10 g L-1 CA + 10 g L-1 CaCl2) consiguió alcanzar un límite de comercialización del producto de 9 días a 5 ºC. La evaluación de distintas atmósferas controladas en combinación con tratamientos antioxidantes (AA o CA), como paso previo al envasado en atmósfera modificada (MAP) del caqui, mostró como más efectiva en el control del pardeamiento enzimático la atmósfera compuesta por 5 kPa O2 (balance N2). Esta atmósfera mantuvo la calidad visual del caqui cortado dentro del límite de comercialización durante 7-9 días a 5 ºC. Por el contrario, la aplicación de altas concentraciones de CO2 (10 ó 20 kPa) dio lugar a un pardeamiento en ciertas zonas de la pulpa que se conoce como 'internal flesh browning'. Estudios posteriores confirmaron el efecto beneficioso del envasado de caqui cortado y tratado con solución antioxidante (CA-CaCl2) en una MAP activa de 5 kPa O2 en la calidad visual del fruto frente a la aplicación de una MAP pasiva. El desarrollo de recubrimientos comestibles con capacidad antioxidante se realizó mediante la incorporación de antioxidantes (10 g L-1 CA + 10 g L-1 CaCl2) a formulaciones a base de proteína de suero lácteo (WPI), proteína de soja (SPI), hidroxipropilmetilcelulosa (HPMC) y pectina. Todos los recubrimientos fueron efectivos controlando el pardeamiento enzimático del caqui cortado, siendo las muestras recubiertas con HPMC y pectina las mejor evaluadas visualmente. En general, el procesado, la aplicación de antioxidantes, el envasado en atmósferas controladas y los distintos recubrimientos comestibles estudiados, si bien no mostraron un efecto claro en los parámetros de calidad nutricional evaluados, no tuvieron un efecto negativo en los mismos. Por otra parte, los frutos cosechados a final de campaña tuvieron mayor actividad antioxidante y contenido en carotenoides. / [CAT] El caqui persimmon (Diospyros kaki L.) 'Rojo Brillante' és un cultiu astringent que presenta unes propietats organolèptiques i nutricionals excel¿lents. En la última dècada, el seu cultiu en l'àrea mediterrània d'Espanya s'ha incrementat de manera exponencial amb el desenvolupament de la tecnologia que permet eliminar l'astringència, mantenint la fermesa del mateix. Esta nova forma de presentació, aporta un gran nombre d'avantatges, entre els quals s'inclou la possibilitat de comercialitzar-lo com fruita fresca processada. No obstant, l'èxit comercial del producte està limitat per pardetjament enzimàtic, la pèrdua de fermesa i el creixement microbià. L'objectiu de la Tesis ha estat en el desenvolupament de caqui 'Rojo Brillante' tallat en fresc mitjançant un enfocament que integra l'estudi de les característiques del producte en el moment del processat i de diferents tecnologies en el manteniment de la qualitat físico-química, sensorial, nutricional i microbiològica del producte durant un període que permeta la seua comercialització. En primer lloc, es va avaluar l'efecte de l'estat de maduresa (MS) en el moment de recol¿lecció, el temps d'emmagatzemament a 15ºC abans del processat i l'aplicació de diferents tractaments antioxidants en el pardetjament enzimàtic i la qualitat sensorial i nutricional del caqui 'Rojo Brillante' tallat i emmagatzemat a 5 ºC. L'aplicació de 10 g L-1 d'àcid ascòrbic (AA) o 10 g L-1 d'àcid cítric (CA) va controlar el pardetjament enzimàtic i va mantenir la qualitat visual del caqui per damunt del límit de comercialització entre 6-8 dies d'emmagatzemament a 5 ºC, depenent del MS. No obstant, l'aplicació d'antioxidants va reduir de manera significativa la fermesa del fruit comparat amb el control. La combinació d'aquestos antioxidants amb 10 g L-1 de CaCl2 va permetre mantenir la fermesa en el mateix rang que les mostres control. En un treball posterior, l'aplicació de 1-metilciclopropeno (1-MCP) va permetre processar caqui emmagatzemat 45 dies a 1 ºC amb una bona fermesa comercial i a més, el tractament antioxidant (10 g L-1 CA + 10 g L-1 CaCl2) va aconseguir un límit de comercialització del producte tallat de 9 dies a 5 ºC. L'avaluació de diferents atmosferes controlades en combinació amb tractaments antioxidants (AA o CA), com a pas previ a l'envasament en atmosfera modificada (MAP) del caqui 'Rojo Brillante, va mostrar com a més efectiva en el control del pardetjament enzimàtic l'atmosfera composta per 5 kPa O2 (balanç N2). Aquesta atmosfera va mantenir la qualitat visual del caqui tallat dins del límit de comercialització durant 7-9 dies a 5 ºC. Per contra, l'aplicació d'altes concentracions de CO2 (10 ó 20 kPa) va donar lloc a un pardetjament en certes zones de la polpa, el qual és conegut com 'internal flesh browning'. Estudis posteriors van confirmar l'efecte beneficiós de l'envasament de caqui tallat i tractat amb solució antioxidant (CA-CaCl2) en una MAP activa de 5 kPa O2 millorant la qualitat visual de la fruita front a l'aplicació de una MAP passiva. El desenvolupament de recobriments comestibles amb capacitat antioxidant es va realitzar mitjançant la incorporació d'antioxidants (CA-CaCl2) en formulacions a base de proteïna de sèrum làctic (WPI), proteïna de soia (SPI), hidroxipropilmetilcel-lulosa (HPMC) i pectina. Tots els recobriments van ser efectius controlant el pardetjament enzimàtic del caqui tallat. No obstant, les mostres recobertes amb HPMC i pectina van ser millor avaluades visualment que la resta de tractaments. En general, el processat, l'aplicació d'antioxidants, l'envasament en atmosferes controlades i els distints recobriments comestibles estudiats, si bé no van mostrar un efecte clar en els paràmetres de la qualitat nutricional avaluats, no van tindre un efecte negatiu en els mateixos. Per altra banda, els fruits recol¿lectats a final de temporada van tenir major activitat antioxidant i contingut en / Sanchís Soler, E. (2016). Effect of processing on the physicochemical, sensory, nutritional and microbiological quality of fresh-cut 'Rojo Brillante' persimmon [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/62588 / TESIS

PhD (Food Science) / Department of Food Science and Technology / Finger millet (FM) [Eleusine coracana] is an underutilised cereal grain used as a food source in South Africa. Increased research interest in FM has span over the years owing to its unique nutritional and bioactive composition. Following the recent interest in natural curative substances over their synthetic counterparts in the treatment of food dependent diseases, FM has shown potential nutraceutical effects. Some important health effects like antidiabetic, antioxidative, anti-inflammatory and antimicrobial properties have been reported in recent trials with FM. In view of the increasing utilisation and application of FM in the region of Thulamela Municipality, Vhembe District of South Africa, two common indigenous FM varieties (brown and dark brown) were obtained and analysed for their physicochemical properties, levels of minerals, phytic acid, phenolic compounds and antioxidant activities. For this process, malted non-alcoholic beverages were produced and analysed for their physicochemical properties, levels of phenolic compounds, and total phenolics and antioxidant activities. FM grains were soaked, germinated and kilned at an interval of 24 h for 96 h, using sorghum as an external reference. Mineral composition of the FM and sorghum samples were analysed using an inductively coupled plasma atomic emission spectroscopy (ICP-AES) and mass spectroscopy (ICP-MS), and atomic absorption spectrometer (AAS). Identification and quantification of phenolic compounds were performed using ultra-performance liquid chromatography mass spectrometer (UPLC-MS). All experiments were performed in triplicate except for the UPLC-MS analysis of the malted non-alcoholic beverages that was done in duplicate. Data were analysed by one way analysis of variance, and the mean values were separated by Duncan’s multiple comparison test using SPSS version 24.0. Data showed that the FM varieties were rich in macro- and micro- or trace elements. The macro-elements calcium, magnesium, potassium, phosphorus and sulphur were found in high amounts ranging from 1597.37 mg/ kg – 6775.03 mg/ kg; iron, zinc, strontium and silicon were found in significant amounts in the range 21.47 mg/ kg – 55.67 iii mg/ kg, copper and boron were found in low amounts (2.2 mg/ kg – 7.7 mg/ kg), along with selenium and cobalt (0.02 mg/ kg – 0.05 mg/ kg). Heavy metals, barium and aluminium were found in the FM varieties. Varietal difference was found to play an important role in the mineral content of the grains during malting. Malting for 24 h reduced mineral content except for sodium. Beyond 48 h of malting, mineral content increased, particularly, for 96 h in FM grain malt. Significant (p < 0.05) increases in the mineral content of FM varieties were noted at 48 h and 96 h of malting. Increase occurred at 72 h of malting for potassium, iron and boron. Malting did not have any effect on the manganese content of the dark brown FM; however, it increased the manganese content at 48 h of malting for brown FM. Malting for 96 h significantly (p < 0.05) reduced sodium content. Consecutive decrease in phytic acid content of the grains was not recorded with durations in malting time. Although statistically significant differences (p < 0.05) were observed, malting did not result in too much change in the physicochemical properties of the grains. Several flavonoids, catechin, epicatechin, quercetin, taxifolin, and hesperitin were isolated, whilst protocatechuic acid was the only phenolic acid detected in the unmalted and malted FM. Increases in catechin, epicatechin and protocatechuic acid were observed for 72 and 96 h malt of brown FM with similar observations recorded for sorghum. Complete loss of taxifolin, catechin, and hesperitin were noted with malting time. FM grains exhibited 2, 2-diphenyl-1-picrylhydrazyl (DPPH), 2, 2՛-azinobis-3-ethylbenzthiazoline-6-sulfonic acid (ABTS) radical scavenging action and iron reducing activities. Increased iron reducing activity alongside ABTS radical scavenging activity was recorded with malting time. A fermentation-time dependent decrease in the pH of the non-alcoholic beverages, with a corresponding increase in sugar content were recorded. A similar decrease was also recorded for the viscosities of the beverages. The FM malt beverages were found to contain a higher amount of citric acid compared to the sorghum malt beverage. A decrease in the citric acid content with fermentation time was noted in the grain malt beverages fermented with Lactobacillus fermentum, particularly for the iv FM beverage. The phenolic compounds detected in the FM malt beverages fermented with the grain microbial flora and Lactobacillus fermentum were protocatechuic acid, catechin and epicatechin. Taxifolin and kaempferol along with the earlier mentioned compounds were detected in the sorghum malt beverage. Catechin was found in higher amount compared to other phenolic compounds in the FM and sorghum malt beverages. FM malt beverages were found to contain a higher amount of total phenolics compared to the beverage prepared from sorghum malt. Fermentation with the grains’ microbial flora and L. fermentum resulted in reduced total phenolics of FM and sorghum malt beverages, particularly after 24 h of fermentation. A fermentation-time dependent decrease in total phenolics of FM beverages fermented with L. fermentum was noted. Fermentation within 24 - 48 h using the grain microbial flora showed higher total individual phenolic compounds for the dark brown FM and sorghum, compared to other fermentation periods. Fermentation of the beverages for 24 h retained a higher amount of the total phenolics compared to other fermentation periods, especially for the L. fermentum beverages. Reduced total phenolic content and antioxidant activity of the beverages were noted at 24 h of fermentation for the two microbial sources. Significant (p < 0.05) increases in total phenolics were observed within 72 – 96 h of fermentation of the brown FM malt beverage with the grains’ microbial flora. Fermentation for 72 h and 96 h with L. fermentum increased the total phenolic content of the brown FM. Increase in total flavonoid content (TFC) of brown FM malt beverage was noted at 72 h fermentation for both microbial sources. Unlike with L. fermentum, no significant (p > 0.05) change in TFC was observed for the dark brown FM beverage after 24 h fermentation with the grains’ microbial flora. Beverages exhibited DPPH, ABTS radical scavenging action and iron reducing activities, which were significantly (p < 0.05) reduced at 96 h fermentation for both microbial sources. The 24 h fermented beverage retained a higher amount of total phenolic and flavonoid contents, and had higher antioxidant activity compared to other fermentation periods for both microbial sources. The study shows that FM is a rich source of essential minerals and v phenolic compounds, and demonstrates that 72 to 96 h of malting has a positive effect on minerals and certain phenolic compounds over the 48 h malting period widely used for preparation of FM malt. The presence of hesperitin in FM grain was established. A new method was developed for the production of FM non-alcoholic beverage with measurable amounts of health-promoting compounds. An ideal fermentation period (24 h) for FM malt non-alcoholic beverage production with enhanced health-promoting compounds, using Lactobacillus fermentum was demonstrated. Fermentation limit (96 h) for production of FM malt beverage using either the grain microbial flora or L. fermentum was confirmed. These findings provide a rationale for increased utilisation of FM as a functional food grain, and its use as malt in production of non-alcoholic beverage for health promotion and wellness. / NRF