Numerical study of wedge supported oblique shock wave-oblique detonation wave transitions

The results of a numerical study of premixed Hydrogen-air flows ignition by an oblique shock wave (OSW) stabilized by a wedge are presented, in situations when initial and boundary conditions are such that transition between the initial OSW and an oblique detonation wave (ODW) is observed. More precisely, the objectives of the paper are: (i) to identify the different possible structures of the transition region that exist between the initial OSW and the resulting ODW and (ii) to evidence the effect on the ODW of an abrupt decrease of the wedge angle in such a way that the final part of the wedge surface becomes parallel to the initial flow. For such a geometrical configuration and for the initial and boundary conditions considered, the overdriven detonation supported by the initial wedge angle is found to relax towards a Chapman-Jouguet detonation in the region where the wedge surface is parallel to the initial flow. Computations are performed using an adaptive, unstructured grid, finite volume computer code previously developed for the sake of the computations of high speed, compressible flows of reactive gas mixtures. Physico-chemical properties are functions of the local mixture composition, temperature and pressure, and they are computed using the CHEMKIN-II subroutines.

Aqueous-phase reforming of renewables for selective hydrogen production in the presence of supported platinum catalysts

The evolution of our society is impossible without a constant progress in life-important areas such as chemical engineering and technology. Innovation, creativity and technology are three main components driving the progress of chemistry further towards a sustainable society. Biomass, being an attractive renewable feedstock for production of fine chemicals, energy-rich materials and even transportation fuels, captures progressively new positions in the area of chemical technology. Knowledge of heterogeneous catalysis and chemical technology applied to transformation of biomass-derived substances will open doors for a sustainable economy and facilitates the discovery of novel environmentally-benign processes which probably will replace existing technologies in the era of biorefinary. Aqueous-phase reforming (APR) is regarded as a promising technology for production of hydrogen and liquids fuels from biomass-derived substances such as C3-C6 polyols. In the present work, aqueous-phase reforming of glycerol, xylitol and sorbitol was investigated in the presence of supported Pt catalysts. The catalysts were deposited on different support materials, including Al2O3, TiO2 and carbons. Catalytic measurements were performed in a laboratory-scale continuous fixedbed reactor. An advanced analytical approach was developed in order to identify reaction products and reaction intermediates in the APR of polyols. The influence of the substrate structure on the product formation and selectivity in the APR reaction was also investigated, showing that the yields of the desired products varied depending on the substrate chain length. Additionally, the influence of bioethanol additive in the APR of glycerol and sorbitol was studied. A reaction network was advanced explaining the formation of products and key intermediates. The structure sensitivity in the aqueous-phase reforming reaction was demonstrated using a series of platinum catalysts supported on carbon with different Pt cluster sizes in the continuous fixed-bed reactor. Furthermore, a correlation between texture physico-chemical properties of the catalysts and catalytic data was established. The effect of the second metal (Re, Cu) addition to Pt catalysts was investigated in the APR of xylitol showing a superior hydrocarbon formation on PtRe bimetallic catalysts compared to monometallic Pt. On the basis of the experimental data obtained, mathematical modeling of the reaction kinetics was performed. The developed model was proven to successfully describe experimental data on APR of sorbitol with good accuracy.

Bio-ethanol valorization towards C4s including 1-butanol over metal modified alumina and zeolite catalysts

Bio-ethanol has been used as a fuel additive in modern society aimed at reducing CO2-emissions and dependence on oil. However, ethanol is unsuitable as fuel supplement in higher proportions due to its physico-chemical properties. One option to counteract the negative effects is to upgrade ethanol in a continuous fixed bed reactor to more valuable C4 products such as 1-butanol providing chemical similarity with traditional gasoline components. Bio-ethanol based valorization products also have other end-uses than just fuel additives. E.g. 1-butanol and ethyl acetate are well characterised industrial solvents and platform chemicals providing greener alternatives. The modern approach is to apply heterogeneous catalysts in the investigated reactions. The research was concentrated on aluminium oxide (Al2O3) and zeolites that were used as catalysts and catalyst supports. The metals supported (Cu, Ni, Co) gave very different product profiles and, thus, a profound view of different catalyst preparation methods and characterisation techniques was necessary. Additionally, acidity and basicity of the catalyst surface have an important role in determining the product profile. It was observed that ordinary determination of acid strength was not enough to explain all the phenomena e.g. the reaction mechanism. One of the main findings of the thesis is based on the catalytically active site which originates from crystallite structure. As a consequence, the overall evaluation of different by-products and intermediates was carried out by combining the information. Further kinetic analysis was carried out on metal (Cu, Ni, Co) supported self-prepared alumina catalysts. The thesis gives information for further catalyst developments aimed to scale-up towards industrially feasible operations.

Concanavalin A-reactive nuclear matrix glycoprotein

The binding capacity of concanavalin A (Con A) to condensed euchromatin and heterochromatin was investigated in chicken erythrocyte nuclei (CEN), mouse liver cells, Zea mays mays meristematic cells and Drosophila melanogaster polytene chromosomes after 4 N HCl hydrolysis to determine whether binding was preferentially occurring in bands and heterochromatin. Dry mass (DM) variation was investigated in CEN by interference microscopy. Feulgen and Con A reactions were employed for all materials to correlate the loci of the two reactions. Quantifications and topological verifications were carried out by video image analysis (high performance cytometry). It was observed that 4 N HCl hydrolysis caused an important DM loss in CEN leaving a level corresponding to the average DNA DM content. In this material, Con A binding was restricted to the nuclear envelope, which reinforces the idea of the absence of a nuclear matrix in these cells. The other cell types exhibited a correspondence of Feulgen-positive and Con A-reactive areas. The Con A reaction was highly positive in the condensed chromatin areas and heterochromatin. This fact led us to speculate that Con A-positive proteins may play a role in the chromatin condensation mechanism, endowing this structure with physico-chemical stability towards acid hydrolysis and contributing to its rheological properties.

The photodynamic and non-photodynamic actions of porphyrins

Porphyrias are a family of inherited diseases, each associated with a partial defect in one of the enzymes of the heme biosynthetic pathway. In six of the eight porphyrias described, the main clinical manifestation is skin photosensitivity brought about by the action of light on porphyrins, which are deposited in the upper epidermal layer of the skin. Porphyrins absorb light energy intensively in the UV region, and to a lesser extent in the long visible bands, resulting in transitions to excited electronic states. The excited porphyrin may react directly with biological structures (type I reactions) or with molecular oxygen, generating excited singlet oxygen (type II reactions). Besides this well-known photodynamic action of porphyrins, a novel light-independent effect of porphyrins has been described. Irradiation of enzymes in the presence of porphyrins mainly induces type I reactions, although type II reactions could also occur, further increasing the direct non-photodynamic effect of porphyrins on proteins and macromolecules. Conformational changes of protein structure are induced by porphyrins in the dark or under UV light, resulting in reduced enzyme activity and increased proteolytic susceptibility. The effect of porphyrins depends not only on their physico-chemical properties but also on the specific site on the protein on which they act. Porphyrin action alters the functionality of the enzymes of the heme biosynthetic pathway exacerbating the metabolic deficiencies in porphyrias. Light energy absorption by porphyrins results in the generation of oxygen reactive species, overcoming the protective cellular mechanisms and leading to molecular, cell and tissue damage, thus amplifying the porphyric picture.

Spatiotemporal Features of Coastal Waters in Southwest Finland

In coastal waters, physico-chemical and biological properties and constituents vary at different time scales. In the study area of this thesis, within the Archipelago Sea in the northern Baltic Sea, seasonal cycles of light and temperature set preconditions for intra-annual variations, but developments at other temporal scales occur as well. Weather-induced runoffs and currents may alter water properties over the short term, and the consequences over time of eutrophication and global changes are to a degree unpredictable. The dynamic characteristics of northern Baltic Sea waters are further diversified at the archipelago coasts. Water properties may differ in adjacent basins, which are separated by island and underwater thresholds limiting water exchange, making the area not only a mosaic of islands but also one of water masses. Long-term monitoring and in situ observations provide an essential data reserve for coastal management and research. Since the seasonal amplitudes of water properties are so high, inter-annual comparisons of water-quality variables have to be based on observations sampled at the same time each year. In this thesis I compare areas by their temporal characteristics, using both inter-annual and seasonal data. After comparing spatial differences in seasonal cycles, I conclude that spatial comparisons and temporal generalizations have to be made with caution. In classifying areas by the state of their waters, the results may be biased even if the sampling is annually simultaneous, since the dynamics of water properties may vary according to the area. The most comprehensive view of the spatiotemporal dynamics of water properties would be achieved by means of comparisons with data consisting of multiple annual samples. For practical reasons, this cannot be achieved with conventional in situ sampling. A holistic understanding of the spatiotemporal features of the water properties of the Archipelago Sea will have to be based on the application of multiple methods, complementing each other’s spatial and temporal coverage. The integration of multi-source observational data and time-series analysis may be methodologically challenging, but it will yield new information as to the spatiotemporal regime of the Archipelago Sea.

Optimization and validation of a methodology to determine total arsenic, As(III) and As(V), in water samples, through graphite furnace atomic absorption spectrometry

The Graphite furnace atomic absorption spectrometry (GF AAS) was the technique chosen by the inorganic contamination laboratory (INCQ/ FIOCRUZ) to be validated and applied in routine analysis for arsenic detection and quantification. The selectivity, linearity, sensibility, detection, and quantification limits besides accuracy and precision parameters were studied and optimized under Stabilized Temperature Platform Furnace (STPF) conditions. The limit of detection obtained was 0.13 µg.L-1 and the limit of quantification was 1.04 µg.L-1, with an average precision, for total arsenic, less than 15% and an accuracy of 96%. To quantify the chemical species As(III) and As(V), an ion-exchange resin (Dowex 1X8, Cl- form) was used and the physical-chemical parameters were optimized resulting in a recuperation of 98% of As(III) and of 90% of As(V). The method was applied to groundwater, mineral water, and hemodialysis purified water samples. All results obtained were lower than the maximum limit values established by the legal Brazilian regulations, in effect, 50, 10, and 5 µg.L-1 para As total, As(III) e As(V), respectively. All results were statistically evaluated.

Conservation of Williams pear using edible coating with alginate and carrageenan

The aim of this study was to evaluate the physical and chemical parameters of Williams pear, stored at 25 ºC for 15 days, with and without edible coating. Edible coatings prepared with alginate 2% and carrageenan 0.5% were tested. The analyses carried out on the samples were: weight loss, pH, soluble solids, firmness, and color. The edible coatings were characterized in terms of mechanical properties, permeability, thickness, and opacity. The results show that the application of edible coatings with carrageenan and alginate in pears influenced physical and chemical characteristics such as weight loss, pH, total soluble solids, color, and firmness of the fruit. However, the alginate coating showed the best results on pear conservation since it had lower water vapor permeability and greater tensile strength, and therefore it can be used as a protective film on these fruits.

Physicochemical and microbiological evaluation of corrientes artisanal cheese during ripening

The aim of this study was to evaluate some physical and chemical parameters (total solids, pH, acidity, fat, acid degree value of fat, salt, protein and nitrogen fractions) and their effects on the beneficial (lactic acid bacteria: LAB) and undesirable microbial populations (coliforms, Escherichia coli, Staphylococcus aureus, moulds, and yeast) during ripening of Artisanal Corrientes Cheese, an Argentinian cow's milk variety, to determine whether a longer ripening period than usual improve its hygienic-sanitary quality. The protein content was much higher than that of other cow's milk cheeses with similar values of fat. The larger peptides showed values three times higher in the 30 day-old cheese than those obtained in the beginning of the process. Staphylococcus aureus and Escherichia coli were detected (3.04 ± 1.48 log10 cfu/g of cheese, 2.21 ± 0.84 log10 MPN/g of cheese) even at 15 and 30 days of ripening, respectively. The distribution of three hundred LAB strains classified to the genus level (lactococci:lactobacilli:leuconostocs) was maintained during the ripening period. The high number of LAB in rennet may have contributed to the fermentation as a natural whey starter, unknown source of LAB for this specific cheese so far. The physicochemical changes that occur during ripening were not big enough to inhibit the growth of undesirable microorganisms.

Characterization of a hydrolyzed oil obtained from fish waste for nutraceutical application

The fish industry generates high volume of waste from fish oil that can have the extraction of its lipids used as nutraceuticals and foods. The objective of this study was to produce unsaturated fatty acids from industrialized fish oil by means of a differentiated hydrolysis process. The samples used were crude fish oil obtained from Campestre industry and characterized through physical-chemical parameters, according to AOCS: acidity, peroxide, saponification, iodine and percentage of free fatty acids and also obtained the fatty acid profile through derivatization method for gas chromatography. The results obtained for the oleochemical indices for refined oil were similar to the data found on the literature. The content of polyunsaturated fatty acids (PUFA) was found of 32,78%, with 9,12% of docosahexaenoic (DHA) and 10,36% of eicosapentaenoic (EPA), regarding monounsaturated fatty acids (MUFA) content was of 30,59% in the hydrolyzed fish oil in relation to refined (20,06%). Thus, it can be concluded that the hydrolysis process used for oils from fish-waste was satisfactory on the production of absolute yield of lipids in the process and significant preservation on the percentages of EPA and DHA, interesting on the production of nutraceuticals and nutrition of aquatic animals, including shrimp in captivity.

Influence of heat treatment on the sensory and physical characteristics and carbohydrate fractions of french-fried potatoes (Solanum tuberosum L.)

AbstractThe aim of this study was to analyze the impact that heat treatment with salts and freezing processes on the sensory, instrumental, and physico-chemical characteristics of fried potatoes of the Monalisa cultivar. The potatoes were blanched in distilled water (P); sodium chloride solution (B1); calcium chloride solution (B2), and a solution with both of these salts (B3). They were then pre-cooked and frozen for 24 hours and for 30 days. After frying, sensory characteristics were analyzed (color, texture, flavor, oiliness), along with overall preference and instrumental determinations of texture, color, and oil content. Further tests were conducted on the sample with the best results in the sensory analysis (B1), along with sample P as a control, to determine granule microstructure, carbohydrate fractions, glycemic index, and glycemic load. Blanching B3, despite reducing oil absorption and providing less oiliness, obtained lesser overall preference. Freezing for 30 days increased the lightness, except for when sodium chloride was used, which intensified the color yellow. The use of sodium chloride did not interfere with the type of starch granules, nor with the formation of resistant starch; however, longer freezing time reduced the glycemic index and concentrated the dietary fiber content. All samples exhibited low glycemic index and moderate glycemic loads.

Effect of different stress conditions on the stability of quercetin-loaded lipid microparticles produced with babacu ( Orbignya speciosa ) oil: evaluation of their potential use in food applications

Lipid micro and nanoparticles have been extensively investigated as carriers for hydrophobic bioactives in food systems because they can simultaneously increase the dispersibility of these lipophilic substances and help improve their bioavailability. In this study, lipid microparticles of babacu oil and denatured whey protein isolate were produced, and their ability to protect quercetin against degradation was evaluated over 30 days of storage. Additionally, the lipid microparticles were subjected to the typical stress conditions of food processing (presence of sucrose, salt, and thermal stresses), and their physico-chemical stability was monitored. The data show that the babacu microparticles efficiently avoided the oxidation of quercetin because 85% of the initial amount of the flavonoid was preserved after 30 days. The particles were notably stable up to a temperature of 70 °C for 10 minutes at relatively high concentrations of salt and sucrose. The type of stirring (mechanical or magnetic) also strongly affected the stability of the dispersions.

The impact of wine closure and packaging type, and light and temperature exposure on the concentration of 3-alkyl-2 -methoxypyrazines and other key constituents of wine

3-alkyl-2-methoxypyrazines (MPs) are grape- and insect-derived odor-active compounds responsible for vegetative percepts that are detrimental to wine quality when elevated. This study tested both the effect of closure/packaging types and light/temperature storage conditions on MPs (isopropyl-, secbutyl-, and isobutyl-MP) in wine. An MP-emiched wine rapidly (after 140 hours) and significantly decreased in MP concentration after natural and synthetic cork contact (immersion of closures in wine). This decrease was greatest with synthetic closures (70% - 89% reduction) and secbutyl-MP. Subsequently storage trials tested the effects of commercial closure/packaging options (natural cork, agglomerate cork, synthetic corks, screwcaps and TetraPak® cartons) on MPs in MP-emiched Riesling and Cabernet Franc over 18 months. Regardless of packaging, isobutyl-MP was the most altered from bottling. Notably, all MP levels tended to decrease to the greatest extent in TetraPak® cartons (~34% for all MPs) and there was evidence of contribution ofisoproyl- and secbutyl-MP from cork-based closures (i.e. ~30% increase in secbutyl-MP after 6 months) or from an unidentified wine constituent. To test the effects of various light/temperature conditions (light exposed at ambient temperature in three different bottle hues, light excluded at ambient temperature and light excluded at a "cellar" temperature (14°C)), MP-emiched Riesling and Cabernet Franc were also analyzed for MP concentrations over 12 months. MPs did not vary consistently with light or temperature. Other odorants and physico-chemical properties were tested in all wines during storage trials and closely agree with previous literature. These results provide novel insights into MPs during ageing, interactions with packaging and storage conditions, and assist in the selection of storage conditions/packaging for optimal wine quality.

Huile de palme rouge au Burkina Faso: Qualité et consommation par les femmes de la zone de production et impact sur leur statut en vitamine A

Dans le cadre de la recherche d’appui à la phase III du projet huile de palme rouge (HPR) au Burkina Faso, une étude de base a porté sur 150 femmes de la zone de production échantillonnées par la méthode aléatoire géographique. Leur statut en vitamine A (VA) a été évalué par HPLC et leurs apports alimentaires par un questionnaire de fréquence de consommation. Les connaissances, les perceptions, les habitudes d’utilisation et de consommation de l’HPR ont été explorées par un questionnaire pré-testé administré au domicile des participantes. Une étude comparative sur la qualité nutritionnelle, physico-chimique, microbiologique et sensorielle de 13 échantillons d’HPR de différentes provenances a été également réalisée. La prévalence de faibles rétinolémies était de 10,7% et les apports en VA provenaient à 90% des aliments d’origine végétale. Seules 5,9% des femmes productrices présentaient une faible rétinolémie, comparativement à 20,8% des femmes non-productrices d’HPR. Les échantillons d’HPR présentaient un profil satisfaisant mais quelques-uns étaient limites au plan microbiologique. En outre, aucun échantillon ne se distinguait nettement selon tous les paramètres de qualité étudiés. Cette étude démontre que les aliments d’origine végétale riches en caroténoïdes provitaminiques A, dont l’HPR qui en est la meilleure source, peuvent permettre d’avoir un statut adéquat en VA. Les risques de contamination de l’HPR au stade de la vente au détail impliquent une sensibilisation et une formation aux pratiques exemplaires de manipulation. Mots clés : Huile de palme rouge, vitamine A, diversification alimentaire, qualité, Burkina Faso.

Développement de techniques analytiques pour la détermination des agents anti-infectieux dans les eaux environnementales

Les agents anti-infectieux sont utilisés pour traiter ou prévenir les infections chez les humains, les animaux, les insectes et les plantes. L’apparition de traces de ces substances dans les eaux usées, les eaux naturelles et même l’eau potable dans plusieurs pays du monde soulève l’inquiétude de la communauté scientifique surtout à cause de leur activité biologique. Le but de ces travaux de recherche a été d’étudier la présence d’anti-infectieux dans les eaux environnementales contaminées (c.-à-d. eaux usées, eaux naturelles et eau potable) ainsi que de développer de nouvelles méthodes analytiques capables de quantifier et confirmer leur présence dans ces matrices. Une méta-analyse sur l’occurrence des anti-infectieux dans les eaux environnementales contaminées a démontré qu’au moins 68 composés et 10 de leurs produits de transformation ont été quantifiés à ce jour. Les concentrations environnementales varient entre 0.1 ng/L et 1 mg/L, selon le composé, la matrice et la source de contamination. D’après cette étude, les effets nuisibles des anti-infectieux sur le biote aquatique sont possibles et ces substances peuvent aussi avoir un effet indirect sur la santé humaine à cause de sa possible contribution à la dissémination de la résistance aux anti-infecteiux chez les bactéries. Les premiers tests préliminaires de développement d’une méthode de détermination des anti-infectieux dans les eaux usées ont montré les difficultés à surmonter lors de l’extraction sur phase solide (SPE) ainsi que l’importance de la sélectivité du détecteur. On a décrit une nouvelle méthode de quantification des anti-infectieux utilisant la SPE en tandem dans le mode manuel et la chromatographie liquide couplée à la spectrométrie de masse en tandem (LC-MS/MS). Les six anti-infectieux ciblés (sulfaméthoxazole, triméthoprime, ciprofloxacin, levofloxacin, clarithromycin et azithromycin) ont été quantifiés à des concentrations entre 39 et 276 ng/L dans les échantillons d’affluent et d’effluent provenant d’une station d’épuration appliquant un traitement primaire et physico- chimique. Les concentrations retrouvées dans les effluents indiquent que la masse moyenne totale de ces substances, déversées hebdomadairement dans le fleuve St. Laurent, était de ~ 2 kg. En vue de réduire le temps total d’analyse et simplifier les manipulations, on a travaillé sur une nouvelle méthode de SPE couplée-LC-MS/MS. Cette méthode a utilisé une technique de permutation de colonnes pour préconcentrer 1.00 mL d’échantillon dans une colonne de SPE couplée. La performance analytique de la méthode a permis la quantification des six anti-infectieux dans les eaux usées municipales et les limites de détection étaient du même ordre de grandeur (13-60 ng/L) que les méthodes basées sur la SPE manuelle. Ensuite, l’application des colonnes de SPE couplée de chromatographie à débit turbulent pour la préconcentration de six anti-infectieux dans les eaux usées a été explorée pour diminuer les effets de matrice. Les résultats obtenus ont indiqué que ces colonnes sont une solution de réchange intéressante aux colonnes de SPE couplée traditionnelles. Finalement, en vue de permettre l’analyse des anti-infectieux dans les eaux de surface et l’eau potable, une méthode SPE couplée-LC-MS/MS utilisant des injections de grand volume (10 mL) a été développée. Le volume de fuite de plusieurs colonnes de SPE couplée a été estimé et la colonne ayant la meilleure rétention a été choisie. Les limites de détection et de confirmation de la méthode ont été entre 1 à 6 ng/L. L’analyse des échantillons réels a démontré que la concentration des trois anti-infectieux ciblés (sulfaméthoxazole, triméthoprime et clarithromycine) était au dessous de la limite de détection de la méthode. La mesure des masses exactes par spectrométrie de masse à temps d’envol et les spectres des ions produits utilisant une pente d’énergie de collision inverse dans un spectromètre de masse à triple quadripôle ont été explorés comme des méthodes de confirmation possibles.