Ce travail présente l’étude d’un procédé de production de 5-hydroxymethylfurfural (HMF), une molécule plateforme prometteuse pour la production de carburants et de polymères biosourcés. La première partie de ce travail a consisté à développer la synthèse du HMF à partir d’hexoses lignocellulosiques dérivés de la biomasse, plus particulièrement du fructose, en milieu diphasique CO2-H2O haute pression, une technologie efficace et respectueuse de l’environnement pour le traitement de la biomasse. À partir d'expériences cinétiques et de leur modélisation, l'effet du CO2 comme catalyseur acide réversible a été évalué. Par ailleurs, le rendement en HMF s'est avéré limité en raison de réactions de dégradation. Un moyen pertinent d’augmenter le rendement en HMF en empêchant sa dégradation a consisté à coupler sa synthèse avec son extraction simultanée par le CO2 supercritique, ce qui a conduit à un procédé de réaction extractive. Dans ce contexte, des coefficients de partage de HMF entre le CO2 supercritique et l’eau ont été évalués expérimentalement, en supposant que l'équilibre soit atteint à tout moment dans le dispositif d'extraction. Les données expérimentales ont permis l’application de modèles thermodynamiques pour décrire le système ternaire CO2-HMF-H2O afin de trouver des conditions de fonctionnement favorables au procédé. Le couplage de la modélisation cinétique et du procédé d'extraction par le CO2, basé sur l'équilibre thermodynamique du mélange, a rendu possible la prédiction des meilleures conditions de fonctionnement du procédé de réaction extractive du HMF à partir de sucres issus de biomasse lignocellulosique. Ce mode de fonctionnement a permis d'exploiter tous les avantages de l'utilisation du CO2 pour les réactions de conversion de la biomasse : catalyseur acide réversible et solvant d'extraction

Extensive consumption of carbon resources has led to decreasing reserves of fossil fuels and growing concern about global warming. This dilemma has promoted a shift in the economy to develop new long-term, environmentally friendly, and sustainable sources for fuels and chemicals to replace fossil fuel-based sources. Renewable biomass is an ideal alternative, as it is abundant, and relatively cheap. Among current biofuel resources, 5-hydroxymethylfurfural (5-HMF) is a versatile intermediate between biomass-based carbohydrate chemistry and fossil fuel-based industrial organic chemistry, which can be used to synthesize a broad range of chemicals that are currently derived from fossil fuel-based resources. Carbohydrates became the preferred feedstock for high yield production of 5-HMF, and the most convenient route for the synthesis of 5-HMF is the acid-catalyzed dehydration of hexose. Within this context, a variety of processes were developed for the synthesis of 5-HMF from dehydration of fructose involving various solvents, including water, organic solvents, and biphasic systems. Likewise, a range of catalysts were employed, such as homogeneous acid catalysts and metal chlorides, which showed high catalytic activity. Heterogeneous catalysts have also been receiving attention due to their advantages such as easy recovery and recyclability. In the current research, microwave-assisted synthesis of 5-HMF by dehydration of fructose over various acidic porous catalysts, such as periodic mesoporous organosilica (PMO), carbon materials, and metal organic frameworks (MOFs), was investigated. The results showed that the obtained 5-HMF yields were satisfactory, and more importantly highlighted some of the properties of porous heterogeneous catalysts that may improve the production of 5-HMF.

A produção de compostos a partir de carboidratos conhecidos como blocos de construção tem despertado muito interesse da comunidade científica recentemente, principalmente em aplicações de bioenergia. Um desses compostos é o 5-hidroximetilfurfural ou HMF, o qual apresenta um alto potencial como matéria-prima na produção de biocombustíveis e produtos químicos de alto valor agregado, como polímeros e fármacos. A principal via para a obtenção de HMF é a desidratação de mono e polissacarídeos em meio ácido em um reator bifásico. A fase aquosa reacional contém um catalisador ácido e um açúcar, e a fase orgânica extrativa é formada por um solvente alcoólico parcialmente miscível com água que extrai continuamente o composto. Uma revisão de literatura revelou que o processo industrial ainda não é economicamente viável principalmente pela falta de dados termodinâmicos de equilíbrio associados à solubilidade durante a etapa extrativa, ou seja, à interação do HMF com água e solventes. Consequentemente, muita energia e reagentes são desperdiçados, juntamente com os coprodutos na tentativa de extrair de forma eficiente o HMF. Neste trabalho, avaliou-se a interação em mistura aquosa entre o HMF e três álcoois de diferentes cadeias carbônicas (1-pentanol, 1-hexanol e 1-heptanol) a temperatura de 25° C. Os coeficientes de distribuição e de seletividade foram empregados para avaliar a capacidade dos solventes de extrair o 5-hidroximetilfurfural da solução aquosa. Os resultados mostraram que o 1-pentanol apresentou melhor desempenho entre os álcoois estudados para a recuperação de HMF a partir da água. Já o modelo NRTL foi usado para correlacionar os dados experimentais e os parâmetros de interação binária relevantes. O desvio médio quadrático da raiz (RMSD) do modelo NRTL foi de 0,78%, o que indica que os dados experimentais do ELL podem ser correlacionados satisfatoriamente pelo modelo. / The building block composts\' production from carbohydrates is currently attracting the attention of the research community, especially because they could be used as bioenergy. One of those composts is 5-hydroximetilfurfural, or HMF, which has a high potential as crude matter in biofuels as well as in medicine and also in polymers\' production. The easiest way to obtain HMF is by oligosaccharides dehydration using an acid medium at a biphasic reactor. In the aqueous phase, there are an acid catalyser and a sugar, and in the extractive organic phase, there is an alcoholic solvent that is partially miscible with water, were HMF is extracted continuously. A literature review showed that the industrial extraction process is not yet economically attractive. That happens due to missing thermodynamic data that would guarantee a successful extraction, such as the liquid-liquid equilibrium (LLE) data from the HMF, water and alcohol system. By improving the LLE in the extraction phase utilising a correct and efficient alcohol, we can increase the system efficiency: more HMF and less unwanted by-products extraction and a decrease in the energy consumption. Having those things in mind, in this research solubility graphics and LLE data between HMF, water, alcohol (1-pentanol, 1-hexanol e 1-heptanol) at 298,15 K and ~0,1 MPa were determined experimentally. The distribution coefficients and selectivities were employed to assess the capacity of solvents to extract 5hydroxymethylfurfural from aqueous solution. 1-pentanol showed better performance than the other studied alcohols for 5-hydroxymethylfurfural recovery from water. The NRTL model was used to correlate the experimental data and relevant binary interaction parameters were regressed. The root mean square deviations (RMSD) of the NRTL model was around 0.78%, which indicate that the experimental LLE data can be successfully correlated by model.

A produção de compostos a partir de carboidratos conhecidos como blocos de construção tem despertado muito interesse da comunidade científica recentemente, principalmente em aplicações de bioenergia. Um desses compostos é o 5-hidroximetilfurfural ou HMF, o qual apresenta um alto potencial como matéria-prima na produção de biocombustíveis e produtos químicos de alto valor agregado, como polímeros e fármacos. A principal via para a obtenção de HMF é a desidratação de mono e polissacarídeos em meio ácido em um reator bifásico. A fase aquosa reacional contém um catalisador ácido e um açúcar, e a fase orgânica extrativa é formada por um solvente alcoólico parcialmente miscível com água que extrai continuamente o composto. Uma revisão de literatura revelou que o processo industrial ainda não é economicamente viável principalmente pela falta de dados termodinâmicos de equilíbrio associados à solubilidade durante a etapa extrativa, ou seja, à interação do HMF com água e solventes. Consequentemente, muita energia e reagentes são desperdiçados, juntamente com os coprodutos na tentativa de extrair de forma eficiente o HMF. Neste trabalho, avaliou-se a interação em mistura aquosa entre o HMF e três álcoois de diferentes cadeias carbônicas (1-pentanol, 1-hexanol e 1-heptanol) a temperatura de 25° C. Os coeficientes de distribuição e de seletividade foram empregados para avaliar a capacidade dos solventes de extrair o 5-hidroximetilfurfural da solução aquosa. Os resultados mostraram que o 1-pentanol apresentou melhor desempenho entre os álcoois estudados para a recuperação de HMF a partir da água. Já o modelo NRTL foi usado para correlacionar os dados experimentais e os parâmetros de interação binária relevantes. O desvio médio quadrático da raiz (RMSD) do modelo NRTL foi de 0,78%, o que indica que os dados experimentais do ELL podem ser correlacionados satisfatoriamente pelo modelo. / The building block composts\' production from carbohydrates is currently attracting the attention of the research community, especially because they could be used as bioenergy. One of those composts is 5-hydroximetilfurfural, or HMF, which has a high potential as crude matter in biofuels as well as in medicine and also in polymers\' production. The easiest way to obtain HMF is by oligosaccharides dehydration using an acid medium at a biphasic reactor. In the aqueous phase, there are an acid catalyser and a sugar, and in the extractive organic phase, there is an alcoholic solvent that is partially miscible with water, were HMF is extracted continuously. A literature review showed that the industrial extraction process is not yet economically attractive. That happens due to missing thermodynamic data that would guarantee a successful extraction, such as the liquid-liquid equilibrium (LLE) data from the HMF, water and alcohol system. By improving the LLE in the extraction phase utilising a correct and efficient alcohol, we can increase the system efficiency: more HMF and less unwanted by-products extraction and a decrease in the energy consumption. Having those things in mind, in this research solubility graphics and LLE data between HMF, water, alcohol (1-pentanol, 1-hexanol e 1-heptanol) at 298,15 K and ~0,1 MPa were determined experimentally. The distribution coefficients and selectivities were employed to assess the capacity of solvents to extract 5hydroxymethylfurfural from aqueous solution. 1-pentanol showed better performance than the other studied alcohols for 5-hydroxymethylfurfural recovery from water. The NRTL model was used to correlate the experimental data and relevant binary interaction parameters were regressed. The root mean square deviations (RMSD) of the NRTL model was around 0.78%, which indicate that the experimental LLE data can be successfully correlated by model.

Ce travail présente l’étude d’un procédé de production de 5-hydroxymethylfurfural (HMF), une molécule plateforme prometteuse pour la production de carburants et de polymères biosourcés. La première partie de ce travail a consisté à développer la synthèse du HMF à partir d’hexoses lignocellulosiques dérivés de la biomasse, plus particulièrement du fructose, en milieu diphasique CO2-H2O haute pression, une technologie efficace et respectueuse de l’environnement pour le traitement de la biomasse. À partir d'expériences cinétiques et de leur modélisation, l'effet du CO2 comme catalyseur acide réversible a été évalué. Par ailleurs, le rendement en HMF s'est avéré limité en raison de réactions de dégradation. Un moyen pertinent d’augmenter le rendement en HMF en empêchant sa dégradation a consisté à coupler sa synthèse avec son extraction simultanée par le CO2 supercritique, ce qui a conduit à un procédé de réaction extractive. Dans ce contexte, des coefficients de partage de HMF entre le CO2 supercritique et l’eau ont été évalués expérimentalement, en supposant que l'équilibre soit atteint à tout moment dans le dispositif d'extraction. Les données expérimentales ont permis l’application de modèles thermodynamiques pour décrire le système ternaire CO2-HMF-H2O afin de trouver des conditions de fonctionnement favorables au procédé. Le couplage de la modélisation cinétique et du procédé d'extraction par le CO2, basé sur l'équilibre thermodynamique du mélange, a rendu possible la prédiction des meilleures conditions de fonctionnement du procédé de réaction extractive du HMF à partir de sucres issus de biomasse lignocellulosique. Ce mode de fonctionnement a permis d'exploiter tous les avantages de l'utilisation du CO2 pour les réactions de conversion de la biomasse : catalyseur acide réversible et solvant d'extraction / This work aims at developing a new production process for 5-hydroxymethylfurfural (HMF), a promising bio-based platform chemical for the production of fuels and renewably sourced polymers. In the first part of this work, synthesis of HMF from lignocellulosic biomass-derived hexoses, and more particularly fructose, was carried out in a two-phase high-pressure CO2-H2O system, regarded as an efficient and eco-friendly technology in biomass processing. From kinetic experiments and their modeling, the effect of CO2 as a potential reversible acid catalyst was assessed. Also, HMF yield was shown to be limited due to sequential degradation reactions. Arelevant way to increase HMF yield by preventing its degradation has consisted in coupling its synthesis with simultaneous extraction by supercritical CO2, leading to a one-pot extractive reaction process. In that context, partition coefficients of HMF between supercritical CO2 and water have been experimentally evaluated, assuming that equilibrium is achieved at any time in the extraction device. Experimental data has enabled the application of thermodynamic models to describe the ternary CO2-HMF-H2O system in order to find favourable operating conditions for the process. Coupling the kinetic modelling with the CO2 extracting process modelling, based on the thermodynamic equilibrium of the mixture, has provided the theoretical tool allowing prediction of the best operating conditions for the one pot extractive process of HMF production from sugars issued from lignocellulosic biomass. This operating mode allowed exploiting all advantages of the use of CO2 for such reactions of biomass conversion: reversible acid catalyst and extracting solvent.

The Knoevenagel reaction was applied to form a carbon-carbon double bond between the aldehydes (HMF, furfual) and an alpha di-carbonyl compound. The alpha di-carbonyl compound used was malonic acid, which can be bio-derived from glucose along fermentation routes. The effects of solvents (THF, water, ethanol, isopropanol, ethyl ether, toluene) and catalysts (e.g. homogeneous and heterogeneous amines, solid basic oxides) on the yields of alpha-beta unsaturated acids were investigated. It was found that the homogeneous amines worked well in THF solvent (90-100% conversion, 99% selectivity for furfural and HMF), while the poly(styrene) supported ethylenediamine gave a higher conversion and selectivity for HMF (65± 5%, 99% selectivity) over furfural (58 ± 7%, 99% selectivity). This trend was also present in competition reactions where both HMF and furfural were reacted in the same vessel. á-â Unsaturated mono-acids for both HMF and furfural were identified as minor side products. However, levulinic acid did not work as well under the conditions studied. Lastly, among the solvents studied, several caused precipitation of the Knoevenagel products.

The main aim of the thesis: Effect of sweetener, temperature and cooking time on the hydroxymethylfurfural selected bakery products, was to determine the amount of hy-droxymethylfurfural in sweeteners and dough and biscuits made from them. Sweeteners used were: wheat syrup, corn syrup, date syrup, honey, sucrose, invert sugar and cane molasses. Three baking temperatures (175°C, 200°C, 225°C) were used. Cookies baked at 200°C and 225°C, were sensorially evaluated. The highest amounts of HMF were found in invert sugar, less amounts in cane molasses and honey. The amounts of HMF were increasing with temperature baking for invert sugar´s biscuits and date syrup´s biscuits. The firmest biscuits, tested by TIRATEST, were biscuits with sucrose baked at 175°C. Biscuits baked at 200°C showed better sensory evaluation of acceptability than the biscuits baked at 225°C. The best overall acceptibility in 200°C exhibited the biscuits with sucrose, the second best were the invert sugar biscuits, followed by the date syrup biscuits.

MACHADO, K. I. A. Desenvolvimento de um método de despeliculamento de amêndoas de castanha de caju tipo “durão” com vapores ácidos e salino. 2013. 63 f. Dissertação (Mestrado em Ciência e Tecnologia de Alimentos) - Centro de Ciências Agrárias, Universidade Federal do Ceará, Fortaleza, 2013. / Submitted by Daniel Eduardo Alencar da Silva (dealencar.silva@gmail.com) on 2015-01-26T17:44:50Z No. of bitstreams: 1 2013_dis_kiamachado.pdf: 1115833 bytes, checksum: 337b38d49bdbb225395b77f2b9ed5836 (MD5) / Approved for entry into archive by José Jairo Viana de Sousa(jairo@ufc.br) on 2016-01-29T20:23:01Z (GMT) No. of bitstreams: 1 2013_dis_kiamachado.pdf: 1115833 bytes, checksum: 337b38d49bdbb225395b77f2b9ed5836 (MD5) / Made available in DSpace on 2016-01-29T20:23:01Z (GMT). No. of bitstreams: 1 2013_dis_kiamachado.pdf: 1115833 bytes, checksum: 337b38d49bdbb225395b77f2b9ed5836 (MD5) Previous issue date: 2013 / One of the biggest challenges that faces the cashew nut processing industries today, is the kernels that needs to peel again, called durao kernels, manually peeled- with a low peeling yield or peeled with conventional water steam - which causes a noticeable browning, decreasing its commercial value. To solve this problem, were performed initially on a laboratory scale, peeled kernels and skin (Ø = 1,68 mm) from kernels were treated with steams from tartaric acid 1,0;2,0;3,0% ; malic acid 1,0;3,0;5,0 % ; potassium chloride 1,0;2,0 3,0% and water during 1,2,3,4 and 5 minutes. Was measured the condensed steam, from treatment of the skin, total phenolics and water soluble pigments. The total phenolics were also measured in the steams after treatment of peeled kernels. In kernel peeled, concentration hydroxymethylfurfural (HMF) and instrumental color, was determined. In this study, in addition to measuring the constituents already mentioned, was extremely important to the understanding of how browning occurs on the surface of kernels, the Maillard reaction and the interactions of the extracted pigments with their steams. The results showed that the lowest concentration of soluble pigments, total phenolics extracted from the skin and less formation of hydroxymethylfurfural in kernels occurred in treatment with tartaric acid 1,0% - 1,0 minute; malic acid 1,0% - 1,0 minute; potassium chloride 2,0% - 1,0 minute and water - 1,0 minute. The peeled and breaking on an industrial scale in kernels durao with skin applying these steams cited in times and concentrations mentioned, showing the following values for the percentages of peeling and breaking, was determined respectively - malic acid: 50,24 - 28,37; tartaric acid: 56,78 - 20,99; potassium chloride: 56,52 - 23,15 and water: 50,43 - 24,12. From the peeled kernel colorimetric analysis (L*, a*, b*) after treatments with the four steams in the times above mentioned, tartaric acid 1,0% - 1,0 minute showed the best values when compared with the colour parameter of the kernel exportation 01- standard. The results still showed that is more profitable to use tartaric acid steam instead of water steam to increase peeling yield and reduce kernel durao breaking. / Um dos maiores problemas atuais da indústria de beneficiamento de castanha de caju, são as amêndoas que necessitam de re-despeliculagem, as amêndoas do tipo “durão”, despeliculadas manualmente, ou com vapor convencional, tendo como inconvenientes a baixa produtividade de raspagem e o escurecimento das amêndoas, fatores depreciativos de preço. Para solucionar esse problema, inicialmente foram realizados em nível de laboratório, ensaios de tratamento de amêndoas despeliculadas e com películas de diâmetro médio Ø = 1,68 mm, com vapores provenientes de soluções de ácido tartárico (1%; 2% e 3%), ácido málico (1%; 3% e 5%), cloreto de potássio (1%, 2% e 3%) e água nos tempos de exposição de 1,2, 3, 4 e 5 minutos. Foram quantificados nos condensados dos vapores, provenientes do tratamento da película, os compostos fenólicos totais e pigmentos hidrossolúveis. Os compostos fenólicos totais também foram quantificados nos vapores após os tratamentos das amêndoas despeliculadas. Nas amêndoas despeliculadas foram determinados a concentração de hidroximetilfurfural (HMF) e a cor instrumental. Neste estudo, além de quantificar os constituintes já citados, foi de extrema importância o entendimento acerca da forma como ocorre o escurecimento na superfície das amêndoas, via reação de Maillard e pela interação dos pigmentos extraídos com esses vapores. Os resultados mostraram que os menores teores de pigmentos solúveis, fenólicos totais extraídos da película e a menor formação de hidroximetilfurfural nas amêndoas ocorreram nos tratamentos com ácido tartárico 1,0% - 1,0 minuto; ácido málico - 1% - 1,0 minuto; cloreto de potássio 2,0% - 1 minuto e água - 1,0 minuto. Foi avaliado também o despeliculamento e a quebra em escala industrial nas amêndoas durão com película aplicando esses vapores citados, nos tempos e concentrações mencionados, mostrando os seguintes valores para as porcentagens de despeliculagem e quebra, respectivamente: ácido málico: 50,24 - 28,37; ácido tartárico: 56,78 - 20,99; cloreto de potássio: 56,52 - 23,15 e água: 50,43 - 24,12. A análise colorimétrica das amêndoas tratadas com vapor de ácido tartárico a 1% - 1 min. mostrou que esta fonte de vapor, foi a que apresentou melhores resultados em todos os parâmetros (L*, a* e b*), quando comparadas as amêndoas padrão tipo 01 tratadas com vapor de água. Os resultados mostraram ainda que é mais vantajoso usar vapor de ácido tartárico em vez de vapor de água para aumentar o rendimento de despeliculagem e reduzir a quebra das amêndoas de castanha de caju tipo “durão”.

Dans cette thèse, on étudie la stabilité orbitale d’états stationnaires de modèles mathématiques de type "Hamiltonian mean-field", dits modèles HMF. Cette étude est d’abord menée d’un point de vue théorique en utilisant des méthodes variationnelles. Puis, elle est menée d’un point de vue numérique en commençant par l’élaboration de schémas conservant exactement des états stationnaires. Le Chapitre 2 présente une étude théorique de la stabilité orbitale des états stationnaires du modèle HMF Poisson. Plus précisément, on prouve la stabilité orbitale d’une grande classe d’états stationnaires solutions du système HMF avec potentiel de Poisson. Ces états stationnaires sont des minimiseurs d’un problème à une, deux ou une infinité de contraintes d’une certaine fonctionnelle. La preuve s’appuie sur une approche variationnelle. Cependant le caractère borné du domaine empêche l’utilisation des techniques usuelles basées sur des invariances d’échelles. On introduit alors de nouvelles méthodes, spécifiques à ce problème, mais demeurant dans l’esprit des outils de réarrangements introduits pour le système de Vlasov-Poisson. En particulier, ces méthodes permettent de considérer un nombre arbitraire de contraintes et aboutissent à un résultat de stabilité pour une grande classe d’états stationnaires. Dans le Chapitre 3, on construit des schémas numériques conservant exactement des états stationnaires donnés. Ces schémas modélisent mieux la propriété de stabilité orbitale que les schémas classiques. Puis, on propose un schéma plus général en construisant un schéma qui conserve tous les états stationnaires des modèles HMF. Pour finir, à l’aide de ces schémas, est menée une étude numérique de la stabilité des états stationnaires du système de HMF Poisson qui vient compléter l’étude théorique du Chapitre 2. / In this thesis, we study the nonlinear orbital stability of steady states of "Hamiltonian mean-field" models, called HMF models. First, this study is being done theoretically by using variational methods. It is then carried out numerically by building numerical schemes wich exactly preserve steady states. Chapter 2 presents a theoretical study of the orbital stability of steady states which are solutions to the HMF Poisson system. More specifically, the orbital stability of a large class of steady states which are solutions to the HMF system with Poisson potential is proved. These steady states are obtained as minimizers of an energy functional under one, two or infinitely many constraints. The proof relies on a variational approach. However the boundedness of the space domain prevents us from using usal technics based on scale invariance. Therefore, we introduce new methods which, although specific to our context, remain somehow in the same spirit of rearrangements tools introduced for the Vlasov-Poisson system. In particular, these methods allow for the incorporation of an arbitrary number of constraints, and yield a stability result for a large class of steady states. In Chapter 3, numerical schemes exactly preserving given steady states are built. These schemes model the orbital stability property better than the classic ones. Then, a more general scheme is introduced by building a scheme wich preserves all steady states of HMF models. Lastly, by means of these schemes, we conduct a numerical study of stability of steady states solutions to HMF Poisson system. This completes the theoretical study in Chapter 2.

Seit langem wird Obst durch Trocknen haltbar gemacht. Dazu werden vorwiegend die Lufttrocknung und Konvektionstrocknungsverfahren eingesetzt. Jedoch werden auch neuere Techniken entwickelt, um die Produktqualität zu steigern oder die Produktion zu verbessern. Von der IBT.InfraBio Tech GmbH in Freiberg wurde die STIR®-Technologie vorgestellt. Diese neue Technologie wird u. a. zum Trocknen von Lebensmitteln eingesetzt. Dazu wird von einem Strahler Infrarotstrahlung eines bestimmten Wellenlängenbereichs abgegeben, der den Absorptionswellenlängen von Wasser sehr ähnlich ist. Dadurch werden Wassermoleküle im Inneren des zu trocknenden Lebensmittels zum Schwingen angeregt, wodurch Wärme entsteht und das Wasser ausgetrieben wird. Somit kommt es nicht nur zu einer erheblichen Energieeinsparung, der Trocknungsprozess nimmt auch weniger Zeit in Anspruch. Es war jedoch zu untersuchen, ob auch die Produktqualität der STIR®-getrockneten Waren einen Vorteil gegenüber den konventionell getrockneten Lebensmitteln bietet. Zur Untersuchung boten sich getrocknete Äpfel an, da für deren Herstellung die STIR®-Technologie bereits kommerziell eingesetzt wurde. Im Handel waren ebenso einige Sorten verschiedener konventionell getrockneter Apfelprodukte erhältlich, welche mit den STIR®-getrockneten Produkten verglichen werden konnten. Dabei wurde der Untersuchungsschwerpunkt auf das Zucker-Abbauprodukt HMF und die qualitätsgebenden Pflanzenphenolen gelegt. Dazu wurde zunächst eine geeignete RP-HPLC-Methode zur Trennung und Detektion der Phenolcarbonsäuren und Flavonoide sowie von HMF erarbeitet, bevor die Extraktion optimiert werden konnte. Mit dieser Methode sollten dann verschiedene frische Äpfel sowie insbesondere mit unterschiedlichen Verfahren getrocknete Äpfel untersucht werden. Daneben wurde die Fähigkeit, Radikale abzufangen, in den Extrakten der verschiedenen frischen und getrockneten Äpfel sowie von diversen Standards, welche im Extrakt erwartet worden waren, analysiert. Zunächst wurden frische Äpfel unterschiedlicher Sorten, aber auch frische Äpfel gleicher Sorten von unterschiedlichen Händlern untersucht. Es konnte gezeigt werden, dass sich die Sorten untereinander stark in ihrem Polyphenolmuster unterschieden, wobei in den einzelnen Stoffklassen immer eine oder zwei Verbindungen in besonders hohen Gehalten auftraten. Dies sind 5 Chlorogensäure und 4-p-Cumaroylchinasäure als Phenolcarbonsäure-Derivate, die Flavanole (-)-Epicatechin und Procyanidin B2, die Phloretin-Glycoside Phloretin-2’-Xyloglucosid und Phloretin-2’-Glucosid und das Flavonol Quercitrin. Diese kamen jedoch immer in unterschiedlichen Mengen und Verhältnissen vor. Die Absolut-Gehalte innerhalb einer Sorte variierten ebenfalls zum Teil erheblich, wobei die relativen Gehalte innerhalb einer Sorte hingegen enger zusammen lagen. Im Verlauf der Lagerung dreier Apfelsorten bei ca. 6 °C wurde zunächst eine Zunahme des Gehaltes an 5-Chlorogensäure sowie bei den Sorten Elstar und Jonagold von (-)-Epicatechin sowie Procyanidin B2 festgestellt. Ab der 22. Lagerungswoche wurde dann eine leichte Abnahme beobachtet. Zum besseren Verständnis des Verhaltens der Polyphenole beim Trocknungsprozess wurden verschiedene Erhitzungsversuche durchgeführt. So wurden Äpfel dreier Sorten über sechs Stunden getrocknet, wobei zum Teil deutliche Abnahmen in den Polyphenolgehalten auftraten. Dies betraf insbesondere die Flavan-(3)-ole sowie deren Dimere, deren Gehalt zum Teil auf weniger als die Hälfte des Ausgangsgehaltes im Frischapfel abnahmen. Die Gehalte der Hydroxyzimtsäurederivate – 5-Chlorogensäure und 4-p-Cumaroylchinasäure – nahmen hingegen nur wenig ab. Daneben waren aber auch Zunahmen z. B. der Kaffeesäure festzustellen, welche u. a. aus 5-Chlorogensäure freigesetzt werden konnte. Unterschiedliche Auswirkungen durch die Erhitzung konnten nicht nur bei den verschiedenen Polyphenolen beobachtet werden. Ebenfalls traten diese bei der Trocknung unterschiedlicher Apfelsorten auf. Besonders die Polyphenole der Sorte Braeburn wurden stärker in ihrem Gehalt verringert. Geeigneter zum Trocknen erscheinen die Sorten Jonagold und Elstar, bei denen es nur zu einer geringen Abnahme im Gehalt infolge der Trocknung kam. Neben dem Abbau der Polyphenole wurde die Bildung des Zuckerabbauproduktes HMF untersucht. Zusätzlich trat eine weitere Verbindung auf, welche sich ebenfalls als ein Zuckerabbauprodukt herausstellte. Diese Verbindung wurde besonders bei saurer Fructose-Erhitzung gebildet und aus dieser Erhitzungslösung isoliert. Durch Vergleich von UV- und Massen-Spektren mit verschiedenen Standards konnte die Verbindung als DDMP identifiziert werden. Zur Quantifizierung des DDMP lag kein Standard definierter Reinheit vor, weshalb die Komponente als HMF berechnet wurde. Generell verhielten sich diese beiden Substanzen im Verlauf der Trocknung ähnlich, wobei DDMP erst im späteren Trocknungsverlauf in größeren Mengen gebildet wurde. Die Gehalte erreichten in der Regel nur ein Drittel bis ein Fünftel des HMF-Gehaltes. Zudem wurden Äpfel der Sorte Jonagold einer Charge unter Versuchsbedingungen mit Konvektionstrocknung mit und ohne Umluft sowie mit STIR®-Trocknung bei verschiedenen Temperaturen und Zeiten getrocknet und deren Gehalte verglichen, wobei immer ein Endwassergehalt von ca. 5 % angestrebt wurde, um ein knackiges und lagerstabiles Produkt zu erzielen. Bei der Konvektionstrocknung ohne Umluft erwiesen sich 80 °C und 4 Stunden am günstigsten, mit Umluft 60 °C und 5 Stunden sowie 80 °C und 1½ Stunden. Eine Trocknung bei 100 °C war hingegen in beiden Fällen unvorteilhaft, da hierbei sowohl die Polyphenolgehalte abnahmen als auch die HMF- und DDMP-Gehalte anstiegen. Für die STIR®-Trocknung erwies sich besonders eine Trocknung bei 60 °C für drei Stunden, auch aufgeteilt auf eine Vortrocknung von 2 Stunden und eine Nachtrocknung von einer Stunde, als günstig. Temperaturen von 75 °C allein oder nur bei der Nachtrocknung wirkten sich sehr ungünstig aus, da hierbei ebenfalls Abnahmen bei den Polyphenolen auf bis zu 40 % des ursprünglichen Gehaltes im Frischapfel sowie deutliche Zunahmen im HMF- und DDMP-Gehalt zu verzeichnen waren. Diese Ergebnisse wurden darüber hinaus durch die abschließend durchgeführten Untersuchungen der Radikalfängereigenschaften mittels DPPH-Test bestätigt. Dabei blieb die Fähigkeit, Radikale abzufangen, bei niedrigeren Trocknungstemperaturen im Vergleich zum Frischapfel besser erhalten als bei hohen Trocknungstemperaturen. Temperaturen von 100 °C bei der Konvektionstrocknung führten zur Abnahme auf bis zu 60 % im Vergleich zum Frischapfel, Temperaturen von 75 °C bei STIR® zur Abnahme von bis zu 50 %. Somit konnte insgesamt gezeigt werden, dass sowohl für die Konvektions- als auch für die STIR®-Trocknung von Äpfeln Parameter zur Produktion eines qualitativ hochwertigen Endproduktes ermittelt werden können. Hierbei spielen neben der optimierten Temperatur und Zeit der Trocknung auch die geeignete Sortenwahl eine entscheidende Rolle.