This diploma thesis deals with chemical analysis of selected frozen, dried and lyophilized fruit, specifically Mirabelle de Nancy, Aronia Nero and blackcurrant varieties Gairn Ben and Ben Lomond. In the theoretical part taxonomy and botanical characteristics of selected fruit are given. Subsequently the utilization of fruit in food industry is described. In common the theoretical part focuses on lyophilisation and drying of fruit and raw food. Further in this part the methods of phenolic substances, anthocyanins, antioxidant capacity and finally ascorbic acid and carbohydrates value measurements are specified. In the experimental part the value were determined measurements of biologically active substances: total phenols, total anthocyanins, antioxidant capacity, ascorbic acid and carbohydrates. For all value measurements were compared the frozen, dried and lyophilised samples of every single fruit. Further, the every sort of fruit were compared to each other. Following the raw food preparaon a product of lyophilised fruit was made.

The allergic disease of asthma is characterized by an infiltration of inflammatory cells to the lung, a process co-ordinated by T-helper (TH) cells. The TH2 cytokine Interleukin (IL)-4 promotes infiltration of eosinophils to sites of inflammation. Eosinophil-selective chemoattractant cytokines (eg. eotaxins) are synthesized by lung epithelial cells. Eotaxin-3 is expressed at high levels in the asthmatic lung, predominantly after IL-4 stimulation. Eotaxin-3 is therefore a marker of inappropriate airway inflammation. Polyphenolic (PP) compounds found in high concentrations in berries may have beneficial effects in inflammatory conditions. Plant and Food Research produced high-PP extracts of blackcurrant (BC) cultivars that were tested for inflammation modulating effects. Since high doses of PPs have been shown to cause cell death, we tested two BC cultivars at a range of concentrations in a cell viability (WST-1) assay. While no toxic effects were attributable to the BC extracts (1-50µg/ml), a dose-related trend in cell death was observed and therefore 10µg/ml was chosen for further experiments Ten BC cultivars were compared for efficacy by measuring eotaxin-3 production in IL-4 stimulated human lung epithelial (A549) cells in vitro. Cells were incubated with BC extracts (10µg/ml) and IL-4 (10ng/ml) for 24 hours. The supernatants were then quantified for eotaxin-3 levels by an enzyme-linked immunosorbent assay (ELISA). All ten BC extracts reduced eotaxin-3 levels after stimulation with IL-4, and six BC extracts were effective by statistically significant levels (P<0.05), (BC cultivars -01, -02, -03, -05, -09 & -10). Of those, BC extracts of four cultivars demonstrated a reduction of more than 65% from the IL-4 stimulated control. In addition, a positive trend in inflammation modulation vs. one anthocyanin (ACN) in the BC extracts was shown. This study has demonstrated the beneficial inflammation modulatory effects of polyphenolic BC extracts, which could be related to cyanidin 3-O-rutinoside content. These results may have therapeutic potential for asthma.

The allergic disease of asthma is characterized by an infiltration of inflammatory cells to the lung, a process co-ordinated by T-helper (TH) cells. The TH2 cytokine Interleukin (IL)-4 promotes infiltration of eosinophils to sites of inflammation. Eosinophil-selective chemoattractant cytokines (eg. eotaxins) are synthesized by lung epithelial cells. Eotaxin-3 is expressed at high levels in the asthmatic lung, predominantly after IL-4 stimulation. Eotaxin-3 is therefore a marker of inappropriate airway inflammation. Polyphenolic (PP) compounds found in high concentrations in berries may have beneficial effects in inflammatory conditions. Plant and Food Research produced high-PP extracts of blackcurrant (BC) cultivars that were tested for inflammation modulating effects. Since high doses of PPs have been shown to cause cell death, we tested two BC cultivars at a range of concentrations in a cell viability (WST-1) assay. While no toxic effects were attributable to the BC extracts (1-50µg/ml), a dose-related trend in cell death was observed and therefore 10µg/ml was chosen for further experiments Ten BC cultivars were compared for efficacy by measuring eotaxin-3 production in IL-4 stimulated human lung epithelial (A549) cells in vitro. Cells were incubated with BC extracts (10µg/ml) and IL-4 (10ng/ml) for 24 hours. The supernatants were then quantified for eotaxin-3 levels by an enzyme-linked immunosorbent assay (ELISA). All ten BC extracts reduced eotaxin-3 levels after stimulation with IL-4, and six BC extracts were effective by statistically significant levels (P<0.05), (BC cultivars -01, -02, -03, -05, -09 & -10). Of those, BC extracts of four cultivars demonstrated a reduction of more than 65% from the IL-4 stimulated control. In addition, a positive trend in inflammation modulation vs. one anthocyanin (ACN) in the BC extracts was shown. This study has demonstrated the beneficial inflammation modulatory effects of polyphenolic BC extracts, which could be related to cyanidin 3-O-rutinoside content. These results may have therapeutic potential for asthma.

The allergic disease of asthma is characterized by an infiltration of inflammatory cells to the lung, a process co-ordinated by T-helper (TH) cells. The TH2 cytokine Interleukin (IL)-4 promotes infiltration of eosinophils to sites of inflammation. Eosinophil-selective chemoattractant cytokines (eg. eotaxins) are synthesized by lung epithelial cells. Eotaxin-3 is expressed at high levels in the asthmatic lung, predominantly after IL-4 stimulation. Eotaxin-3 is therefore a marker of inappropriate airway inflammation. Polyphenolic (PP) compounds found in high concentrations in berries may have beneficial effects in inflammatory conditions. Plant and Food Research produced high-PP extracts of blackcurrant (BC) cultivars that were tested for inflammation modulating effects. Since high doses of PPs have been shown to cause cell death, we tested two BC cultivars at a range of concentrations in a cell viability (WST-1) assay. While no toxic effects were attributable to the BC extracts (1-50µg/ml), a dose-related trend in cell death was observed and therefore 10µg/ml was chosen for further experiments Ten BC cultivars were compared for efficacy by measuring eotaxin-3 production in IL-4 stimulated human lung epithelial (A549) cells in vitro. Cells were incubated with BC extracts (10µg/ml) and IL-4 (10ng/ml) for 24 hours. The supernatants were then quantified for eotaxin-3 levels by an enzyme-linked immunosorbent assay (ELISA). All ten BC extracts reduced eotaxin-3 levels after stimulation with IL-4, and six BC extracts were effective by statistically significant levels (P<0.05), (BC cultivars -01, -02, -03, -05, -09 & -10). Of those, BC extracts of four cultivars demonstrated a reduction of more than 65% from the IL-4 stimulated control. In addition, a positive trend in inflammation modulation vs. one anthocyanin (ACN) in the BC extracts was shown. This study has demonstrated the beneficial inflammation modulatory effects of polyphenolic BC extracts, which could be related to cyanidin 3-O-rutinoside content. These results may have therapeutic potential for asthma.

Abstract Blackcurrants (Ribes nigrum L.) are widely consumed due to their favourable taste and health-promoting effects. The berries and extracts from different parts of the plant show anticarcinogenic, antioxidative and anti-inflammatory properties, and are effective in reducing the risk of cardiovascular disease and in promoting brain health. These health-promoting benefits are due to high concentrations of valuable compounds such as anthocyanins and flavonols in blackcurrants. However, these compounds are sensitive to heat and processing and some are lost when the berries are processed into products such as jams, purees and juices. Industrial processing of juices is a multistep process that typically includes enzyme treatment, pressing, pasteurisation, clarification and usually also thermal concentration. Alternative minimal processing technologies are required to preserve the health-promoting compounds in products by avoiding the use of high temperatures and extensive clarification. Integrated membrane technology, i.e. combined ultrafiltration and reverse osmosis, was used in this thesis for the production of blackcurrant juice concentrate. Pre-treatment methods, such as enzymatic treatment, ultrafiltration, enzymatic treatment combined with ultrafiltration and centrifugation to increase the filtration efficiency in reverse osmosis were evaluated. Processing was modelled to define the resistances, using the resistance-in-series model. The preservation and concentration of anthocyanins and flavonols were analysed. The results indicated that the main resistance in the reverse osmosis process was polarisation resistance, while membrane resistance was lower and fouling resistance was one order of magnitude lower than the other resistances. The filtration efficiency results showed that the highest flux was achieved by ultrafiltered blackcurrant juice, but that the resulting juices were substantially lower in anthocyanins and flavonols, which were retained on the ultrafiltration membrane. Therefore, replacing ultrafiltration with centrifugation as the clarification method for juices is recommended. Value-added processing of blackcurrant was conceptualised by valorisation of the marc left in the berry pressing process for extraction of anthocyanin compounds. Conventional extraction was compared with microwave-assisted extraction (MAE), with the latter optimised using response surface methodology to achieve maximum efficiency in extracting anthocyanins. The optimum parameters found for MAE were: microwave power 700 W, extraction time 10 minutes, pH 2 adjusted with hydrochloric acid and a solid to solvent ratio of 0.05. Conventional extraction showed the best results when carried out at 80 &#176;C for 300 minutes in aqueous solution with pH 2 adjusted by hydrochloric acid. Under these conditions, recovery of anthocyanins was still 10% lower than with MAE for only 10 minutes of extraction time. / Tiivistelmä Mustaherukoita käytetään paljon niiden hyvän maun ja terveyttä edistävien vaikutusten ansiosta. Marjoilla ja marjakasvin eri osien uutteilla on osoitettu olevan antikarsinogeenisia, antioksidatiivisia ja tulehduksia estäviä ominaisuuksia ja ne ovat tehokkaita pienentämään sydän- ja verisuonisairauksia. Ne edistävät myös aivojen terveyttä. Marjojen arvokkailla yhdisteillä kuten antosyanideillä ja flavonoleilla on terveyttä edistäviä vaikutuksia. Mustaherukassa on runsaasti näitä yhdisteitä. Hillojen, soseiden ja mehujen prosessoinnissa menetetään näitä hyödyllisiä yhdisteistä, koska ne ovat herkkiä lämmölle ja prosessoinnin vaikutuksille. Mehujen prosessoinnissa käytetään entsyymikäsittelyjä, puristusta, pastörointia, selkeytystä ja usein myös lämpökonsentrointia. Tuotteiden terveyttä edistävien yhdisteiden säilyttämiseksi tarvitaan uudenlaisia hellävaraisia prosessointitekniikoita ilman korkeita lämpötiloja ja voimakasta selkeyttämistä. Tässä työssä tutkittiin yhdistettyjen kalvotekniikoiden kuten ultrasuodatuksen ja käänteisosmoosin käyttöä mustaherukkatiivistemehun prosessoinnissa. Esikäsittelymenetelmiä, mm. entsyymikäsittelyä, ultrasuodatusta, entsyymikäsittelyn ja ultrasuodatuksen yhdistelmää sekä sentrifugointia, arvioitiin käänteisosmoosin suodatustehokkuuden parantamisessa. Suodatusvastuksen määrittämiseksi prosessi mallinnettiin käyttäen sarja -vastus mallia. Antosyanidien ja flavonolien säilyminen ja konsentroituminen prosesseissa määritettiin. Tulokset osoittivat, että suurin vastus käänteisosmoosissa aiheutui polarisaatiovastuksesta, kun taas kalvon vastus oli pienempi. Mallinnus osoitti myös, että likaantumisen aiheuttama vastus oli yhtä magnitudia alhaisempi kuin muut vastukset. Suodatusteho osoitti, että suurin virtaus saavutettiin ultrasuodatetulla mustaherukkamehulla. Ultrasuodatetussa mehussa oli kuitenkin huomattavasti vähemmän antosyaniineja ja flavonoleja, mikä johtui näiden yhdisteiden tarttumisesta ultrasuodatuskalvoon. Näin ollen, tämän työn tulokset suosittelevat ultrasuodatuksen korvaamista sentrifugoinnilla mehun kirkastusprosessissa. Mustaherukkamehun tuotannossa muodostuu sivutuotteena ns. puristekakkua, joka sisältää runsaasti antosyaaneja. Työssä kehitettiin antosyaanien talteenottoa tästä sivutuotteesta vertaamalla tavanomaista uuttotekniikkaa mikroaaltoavusteiseen uuttoon. Prosessi optimoitiin vastepintamenetelmällä mahdollisimman suuren antosyaanien uuttotehokkuuden saavuttamiseksi. Optimaaliset parametrit saatiin mikroaaltoavusteisessa uutossa teholla 700 W, uuttoajalla 10 minuuttia, kiintoaines-liuotin -suhteella 0,05 pH-arvossa 2, mikä saavutettiin lisäämällä suolahappoa. Tavanomaisessa uutossa parhaat antosyaanisaannot saavutettiin suolahappo-vesiliuoksella pH-arvossa 2 uuttamalla 300 minuuttia lämpötilassa 80 &#176;C. Antosyaanisaanto oli kuitenkin tavanomaisessa uutossa optimiolosuhteissa 10% pienempi kuin mikroaaltoavusteisessa uutossa 10 minuutin uuttoajalla.

Ce travail porte sur la production de bio-huile par liquéfaction hydrothermale de résidus agroalimentaires, réalisée en réacteur batch. L’objectif est d’étudier l’influence des paramètres opératoires sur la production de bio-huile, et de contribuer à la compréhension des mécanismes de conversion hydrothermale de la biomasse. La liquéfaction hydrothermale des résidus agroalimentaires a été étudiée à partir de l’exemple des drêches de cassis, résidus de pressage des baies. Une étude paramétrique a évalué l’influence de la température, du temps de réaction, de la concentration de biomasse et de l’ajout d’hydroxyde de sodium sur le rendement des produits. Cette étude a permis d’identifier des conditions opératoires favorables à la production de bio-huile, dont le rendement peut notamment bénéficier du recyclage de la phase aqueuse en tant que solvant réactionnel (rendement maximal de bio-huile : 31 %). La caractérisation physico-chimique de la bio-huile montre que celle-ci possède certaines propriétés proches du pétrole brut et de certains fiouls lourds, notamment grâce à sa faible teneur en oxygène en comparaison des huiles de pyrolyse. La bio-huile peut être considérée comme un bio-pétrole brut, mais nécessite toutefois un raffinage conséquent avant de potentielles applications. La conversion hydrothermale de molécules modèles, sélectionnées à partir de l’analyse de la composition des drêches de cassis, a été étudiée à une température de 300 °C et un temps de réaction de 60 min. Cinq monomères modèles (glucose, xylose, acide glutamique, guaiacol et acide linoléique) et deux polymères modèles (cellulose microcristalline et lignine alkali) ont été choisis pour cette étude. Une méthodologie basée sur les plans d’expérience de mélange a été mise en œuvre, afin d’aboutir à la construction de schémas réactionnels, et à l’élaboration de corrélations modélisant les rendements des produits en fonction de la composition initiale des mélanges. L’analyse des produits montre que la conversion hydrothermale des résidus agroalimentaires résulte principalement de dégradations primaires et d’interactions binaires entre les composants de la biomasse. Les corrélations obtenues à partir des composés modèles permettent de décrire avec un bon accord les rendements des produits de conversion hydrothermale de mélanges modèles et de plusieurs résidus agroalimentaires : drêches de brasserie, marc de raisin et akènes de framboise. / This work presents a study of hydrothermal liquefaction of food processing residues using a batch reactor, to produce bio-oil. The objective is to study the influence of operating conditions on bio-oil production, and to contribute to the understanding of the reaction mechanisms occurring during hydrothermal conversion of biomass. Hydrothermal liquefaction of food processing residues was studied using blackcurrant pomace, a berry pressing residue, as an example. A parametric study evaluated the influence of temperature, holding time, biomass concentration and the use of sodium hydroxide as additive on the yields of products. This study allowed the identification of favorable operating conditions to produce bio-oil. The bio-oil yield can in particular benefit from recycling the aqueous phase as reaction solvent (maximum bio-oil yield: 31%). Physicochemical characterization of the bio-oil showed that it has some similarities with heavy crude oil and heavy oils, especially thanks to a lower oxygen content than pyrolysis oils. The bio-oil can be considered as a bio-heavy crude oil, but it still requires significant upgrading before any potential applications. Hydrothermal conversion of model molecules, selected from the characterization of blackcurrant pomace, was studied at a temperature of 300 °C and a holding time of 60 min. Five model monomers (glucose, xylose, glutamic acid, guaiacol and linoleic acid) and two model polymers (microcrystalline cellulose and alkali lignin) were chosen for this study. A mixture design of experiments methodology was followed, to combine reactivity studies with the elaboration of correlations describing the mass yields of products as a function of the initial mixture composition. Analysis of the products shows that hydrothermal conversion of food processing residues is mainly due to degradations of individual compounds and binary interactions between components of biomass. The correlations obtained from the model compounds describe with good accuracy the mass yields of the products from hydrothermal conversion of a model mixture and several food processing residues: brewer’s spent grains, grape marc and raspberry achenes.

Dans le cadre de la présente thèse, a été étudié l’impact de la texturation par traitement thermo-mécanique DIC (Détente Instantanée Contrôlée) sur le séchage de divers produits alimentaires. Ce prétraitement a induit une amélioration de la cinétique de l’opération de séchage quand elle est limitée par le transfert interne de la matière couplé au rétrécissement du produit. Ainsi, la diminution du temps de séchage a atteint 67% dans le cas de l’oignon et 77% dans le cas du cassis. Quant à la diffusivité effective Deff, elle a augmenté par rapport à la matière première jusqu’à 246% pour les pépins et 795% pour les déchets de canneberge, 336% pour l’oignon et 1223% pour le cassis. Dans le cas des produits étudiés, la pression de vapeur de traitement DIC a généralement un effet significatif positif sur la cinétique de séchage et d’extraction des différentes molécules. Concernant les caractérisatiques des produits, nous constatons l’impact positif du traitement par DIC quant aux principales caractéristiques de la matière. Ainsi, les composés phénoliques apparaissent plus disponibles à la suite du traitement adéquat par DIC. Le contenu en composés phénoliques et la capacité antioxydante étant supérieurs dans les produits traités par DIC, la qualité nutritionnelle s’est ainsi également trouvée améliorée. Avec une dégradation thermique négligeable, le traitement DIC implique un effet mécanique dû à la détente instantanée, ce qui permet la rupture de certaines structures cellulaires de la matière et l’augmentation de la quantité maximale extractible. Les caractéristiques physiques diverses (masse volumique apparente et taux relatif d’expansion), les caractéristiques microstructurelles (mesurées par microscopie électronique à balayage) et fonctionnelles d’interaction avec l’eau (réhydratation, teneur en eau, isotherme de sorption, microbiologie et contenu nutritionnel...) peuvent être optimisées en fonction des conditions opératoires DIC, selon les besoins du consommateur. / The present PhD work concerns the effect of thermo-mechanical texturing by DIC (Instantaneous Controlled Pressure-Drop) on fruit and vegetable drying. This pretreatment dramatically improves drying kinetics when the internal mass transfer coupled to the shrinkage of the product, is the limiting process. Indeed, the drying time decreased by 67% in the case of onion and 77% for blackcurrants, while the effective diffusivity Deff increased up to 246%, 795%, 336%, and 1223% for cranberry seed and waste, onion and blackcurrants, respectively. With these products, the saturated steam pressure generally has a significant positive effect on the drying kinetics.DIC treatment significantly improves the main nutritional and functional characteristics of the fruits and vegetables, with more available phenols and higher antioxidant activity. As thermal degradation is negligible, the DIC treatment involves micromechanical effect linked to the instant pressure drop, which allows cell to break and structure to be more porous such increasing the maximum extractable amount. Various physical, microstructural and functional characteristics of new textured material allow water interaction to be completely modified in terms of rehydration kinetics and capacity, sorption isotherm, microbiological and nutritional content... depending on operating DIC conditions, which can be optimized according to the consumer needs.