The research reported here is a study of detector systems to determine those most suited for simultaneous organic acid, inorganic anion determination. Comparisons are made on the basis of detection limits and sensitivities for conductivity, UV/Vis, photoconductivity, and derivative conductivity detection systems. The investigation was made using a constant chromatographic system with the only variable component being the detector system. Eluant optimization conditions for each detector are reported along with tables reporting detection limits and sensitivities for each detector system. Various chromatograms are also shown to provide a visual comparison between detector results.

CONTEXTE GENERAL: En raison des activités anthropiques, les sols sont souvent contaminés par des métaux lourds et des hydrocarbures pétroliers. Le nombre important de sites multi-contaminés dans l'environnement met en lumière la nécessité de trouver des solutions adéquates à ces scénarios complexes d'assainissement, qui, de plus, sont rarement étudiés. Parmi les techniques d'assainissement biologique, la phytoremédiation est une technique qui se base sur les propriétés naturelles des plantes pour assainir les sols. L'utilisation conjointe des plantes et des microorganismes pour dépolluer les sols multi-contaminés est une stratégie de traitement en plein essor. Cependant, l'obstacle majeur qui entrave la réussite de tels traitements est la faible biodisponibilité des polluants dans le sol. Par conséquent, la phytoremédiation peut être assistée par des traitements chimiques et/ou biologiques afin de surmonter cette limitation et d'améliorer l'efficacité de l'assainissement. Dans cette étude, l'approche chimique implique l'ajout d'amendements biodégradables. Enfin, la stratégie biologique retenue dans ce travail est la bioaugmentation qui consiste à ajouter dans le sol des bactéries capables d'améliorer l'assainissement des polluants et/ou favoriser la croissance des plantes. PRINCIPAUX OBJECTIFS: a) Étudier le potentiel de la luzerne pour la phytoremédiation des sols multi-contaminés, b) Étudier les effets de l'acide organique de faible poids moléculaire acide citrique et le tensioactif Tween® 80 sur le processus de phytoremédiation et c) Étudier l'effet de la bioaugmentation avec la bactérie Pseudomonas aeruginosa sur le processus de phytoremédiation. METHODES: Détermination des taux de germination et de mortalité, évaluation des paramètres physiologiques des plantes. Quantification de la biomasse végétale, des métaux lourds dans les plantes, hydrocarbures pétroliers totaux (HCT) dans le sol, et indicateurs microbiologiques du sol. Calcul des paramètres de phytoremediation.RESULTATS REMARQUABLES: La luzerne a présenté une faible tolérance aux HCT du sol à 8400 mg kg-1 de matière sèche (MS). Celle-ci qui a été améliorée lorsque les HCT étaient présents à plus faible concentration (3600 mg kg-1 MS). La luzerne a été en mesure de prendre les métaux dans une proportion limitée (<100 mg kg-1 MS), tandis qu'elle a eu un effet positif sur le nombre de microorganismes du sol capables de dégrader les alcanes et sur l'activité de la lipase dans la rhizosphère. En outre, l'application combinée de l'acide citrique et du Tween® 80 a donné lieu à une amélioration plus importante de nombre et de l'activité microbienne dans la rhizosphère. La bioaugmentation avec P. aeruginosa a eu un effet sur l'amélioration de la biomasse de luzerne (augmentation de la biomasse végétale sèche totale de 71%). En outre, les taux les plus élevés d'élimination des HCT (68%, après 90 jours d'expérience) ont été obtenues dans les sols plantés avec la luzerne et bioaugmentées par P. aeruginosa. CONCLUSION GENERALE: La luzerne pourrait tolérer le sol co-contaminé par des métaux lourds et des hydrocarbures pétroliers, ce qui est une caractéristique essentielle en phytoremédiation. La luzerne ne peut cependant pas être considérée comme une espèce capable d'extraire activement les métaux lourds, même en présence d'amendements chimiques ou par bioaugmentation. Néanmoins, l'augmentation du nombre et de l'activité microbienne dans la rhizosphère a confirmé le potentiel de cette plante à être utilisée avec succès dans le traitement des hydrocarbures pétroliers. Ces effets ont été par ailleurs renforcés par l'application conjointe d'acide citrique et de Tween® 80. Enfin, la combinaison de la phytoremédiation et de la bioaugmentation semble une approche prometteuse pour réaliser l'assainissement des hydrocarbures pétroliers, lorsqu'ils sont présents dans des sols multi-contaminés / GENERAL BACKGROUND : As a result of anthropogenic activities, soil resources remain contaminated with heavy metals and petroleum hydrocarbons. The high frequency of occurrence of multi-contaminated soils in the environment brings to light the necessity to find remediation solutions adequate in such complex scenarios, which besides have seldom been studied. Phytoremediation is a biologically based remediation technology, which takes advantage of the intrinsic physiological abilities of plants to remediate contaminated media. Plants and their associated microorganisms perform phytoremediation processes (e.g. phytoextraction and rhizodegradation), which can bring about the clean-up of multi-contaminated soils. However, a major constraint which hinders the success of phytotechnologies is low bioavailability of pollutants in soil. As a result, chemically- and biologically-assisted phytoremediation are possible strategies used to overcome this limitation and improve the remediation efficiency. The chemical approach presented in this study involves the addition of biodegradable soil amendments to increase the ability of contaminants to be transferred from a soil compartment to plants and microorganisms. The biological strategy explored herein consists of inoculating contaminated soils with bacteria (bioaugmentation) able to improve remediation of pollutants and/or promote plant features.MAIN OBJECTIVES: a) To investigate the phytoremediation potential of alfalfa (Medicago sativa) in multi-contaminated soils b) To study the effects of the low molecular weight organic acid citric acid and the surfactant Tween® 80 on the phytoremediation process c) To assist phytoremediation with a bioaugmentation approach using Pseudomonas aeruginosa bacteria. METHODOLOGIES: Determination of germination and mortality rates, assessment of plant physiological parameters. Quantification of plant biomass, heavy metals in plants, total petroleum hydrocarbons (TPH) in soil, soil microbiological indicators. Calculation of phytoremediation parameters. REMARKABLE RESULTS : Alfalfa presented low tolerance to TPH contaminated soil at 8400 mg kg-1 soil, which was improved when TPH were present at lower concentration (3600 mg kg-1 soil). Alfalfa was able to take up metals to a limited extent (<100 mg kg-1 dry matter), while had a positive effect in promoting microbial number of alkane degraders and lipase activity in the rhizosphere. Moreover, the combined application of citric acid and Tween® 80 resulted in a greater improvement of these parameters. Bioaugmentation with P. aeruginosa had a promoting effect on alfalfa biomass (71% increase of plant total dry biomass). In addition, the highest TPH removal rates (68%, after 90 days of experiment) were obtained in soils vegetated with alfalfa and bioaugmented with P. aeruginosa.OVERALL CONCLUSION: Alfalfa could tolerate a heavy metal and petroleum hydrocarbon co-contaminated soil (subject to TPH levels), which is an essential characteristic for any plant species to be used in phytoremediation. Alfalfa could not be considered as an actively heavy metal removal species as it was not able to phytoextract significant amounts of heavy metals (still in the presence of soil amendments or bioaugmentation). Nevertheless, the enhancement of microbial number and activity in the rhizosphere encouraged the potential of this plant species to be successfully used in the remediation of petroleum hydrocarbons. These effects were additionally enhanced by the joint application of soil amendments. Finally, the combination of phytoremediation and bioaugmentation seems a promising approach to achieve the remediation of petroleum hydrocarbons, when present in multi-contaminated soils

Les bactéries jouent un rôle important dans le fonctionnement des sols et participent activement à l'altération des silicates. L'altération des silicates contrôle en partie la lixiviation d'éléments minéraux majeurs essentiels en solution (maintien de la fertilité des sols). Cependant, si les principaux processus d'altération des silicates sont bien connus en milieu aérobie (acidolyse et complexolyse), cette fonction d'altération bactérienne des silicates n'a jamais été utilisée comme indicateur biologique de la fertilité des sols. Le premier objectif de ce travail de thèse a donc été d'identifier les processus d'altération de 2 micas par des bactéries hétérotrophes en utilisant un modèle d'altération empirique basé sur l'activité des protons et ligands pour identifier et étudier les interactions entre les bactéries et les minéraux. Le traçage des processus d'altération par les isotopes stables du Mg a également été testé. Le second objectif a été de corréler la fonction d'altération de communautés bactériennes aux conditions naturelles rencontrées dans différents sols. Ce travail confirme que l'oxydation partielle du glucose en acides organiques est le mécanisme prédominant par lequel les bactéries amplifient la lixiviation d'éléments en condition aérobie lors de l'altération de la biotite et de la phlogopite, surtout pour des pH proches de la neutralité. Le modèle empirique utilisé a été adapté pour permettre de comparer les taux de libération initiaux du fer lors de l'altération abiotique et bactérienne de micas afin d'identifier les 2 processus majeurs impliqués. Cette approche a permis de mettre en évidence des phénotypes d'altération en fonction du métabolisme, la compétence des souches bactériennes utilisées et des conditions expérimentales. L'étude menée avec les isotopes stables du Mg comme traceurs d'altération n'a pas montré de fractionnements signant chaque processus. L'utilisation du modèle a ensuite permis de montrer que le potentiel d'altération des silicates par les communautés bactériennes dépend de leur origine et en particulier des teneurs en MO et en nutriments des horizons de sols échantillonnés. Deux stratégies d'altération des silicates par ces communautés ont été mises en évidence : (1) les communautés bactériennes isolées des horizons riches en nutriments libèrent peu d'acides organiques, mais très complexants (stratégie K), (2) les communautés isolées d'horizons pauvres en nutriments libèrent beaucoup d'acides organiques peu complexant (stratégie r). L'approche interdisciplinaire proposée dans ce travail permet d'identifier et de caractériser les processus d'altération de phyllosilicates par des bactéries et offre un outil d'identification fonctionnel prometteur pour évaluer la qualité des sols / The bacteria play an important role in soil functioning and are also involved to the weathering of silicate minerals. The silicate weathering controlled the leaching of essential major mineral elements in solution, essential to maintaining soil fertility. However, although the main weathering processes of silicates are well known in aerobic (the proton- and ligand-promoted dissolution), this function of bacterial weathering of silicate minerals has never been used as a biological indicator of soil fertility. The first aim of this work was therefore to identify the process of weathering in two phyllosilicates by heterotrophic bacteria, using an empirical model of silicates weathering based on the activity of protons and ligands to identify and study the interactions between bacteria and minerals. Tracing of weathering processes by isotopic approach using stable isotopes of Mg has also been tested. The second aim was to correlate the “silicate weathering” function of bacterial communities of various soils in field conditions. This study confirms that the partial oxidation of glucose to organic acids is the predominant mechanism by which bacteria accelerate the leaching of elements under aerobic conditions during the weathering of biotite and phlogopite especially at pH close to neutrality. The empirical model used has been adapted to compare the initial release rate of iron in bacterial and abiotic weathering of micas to identify the two major processes involved. This approach highlighted the identification of phenotypes according to the metabolism and the competence of the bacterial strains used. The study with stable isotopes of Mg as tracers of weathering showed no fractionation during the proton- and ligand-promoted dissolution. Using the model in the second part of this work showed that the silicate weathering potential by microbial communities depends on their origin and in particular the contents of OM and nutrients of soil horizons sampled. Two strategies of silicate weathering in these communities have been identified: (1) the bacterial communities isolated from nutrient-rich horizons released few organic acids, but very chelating (strategy K), (2) communities isolated from nutrient-poor horizons release many low chelating organic acids (strategy r). The interdisciplinary approach proposed in this work to identify and characterize the weathering of phyllosilicates by soil heterotrophic bacteria or communities in different environments. It provides a original and promising tool for identifying functional to evaluate the quality of natural soils

A matéria orgânica do solo (MOS) é composta de uma mistura complexa e heterogênea de compostos orgânicos, sendo as substâncias húmicas (SH) a fração mais recalcitrante da MOS. As SH têm grande influência sobre as propriedades químicas e biológicas do solo, contribuindo como fonte de energia para microrganismos e também contribuindo com a disponibilidade de nutrientes. Além disso, as SH podem contribuir de forma expressiva para o desenvolvimento e produção das plantas cultivadas. Neste sentido, o objetivo deste trabalho foi avaliar a atividade e diversidade da comunidade bacteriana do solo, a disponibilidade de nutrientes e a produtividade da cultura de trigo após aplicação de doses crescentes de SH. Dois experimentos foram montados e avaliados, sendo um ensaio de incubação com um solo arenoso e outro um experimento de casa de vegetação com plantas de trigo em dois solos tropicais distintos (textura arenosa e argilosa). Houve um estímulo à atividade microbiana em ambos os experimentos, sendo este estímulo transitório, o que provavelmente ocorreu devido a um efeito priming provocado pela adição de SH. No entanto não houve alteração na estrutura da comunidade bacteriana pela adição de SH, o que pode ser devido ao fato de ser um material recalcitrante e já presente no solo. Também houve aumento na disponibilidade de fósforo, potássio, cálcio e nitrogênio, bem como da CTC, tanto em solo arenoso quanto argiloso, expressando o efeito das SH na melhoria das propriedades químicas de solos tropicais. Além disso, um efeito significativo foi visto em parâmetros relacionados à produtividade do trigo. Houve aumento de massa seca de raízes e parte aérea, além de aumento no peso e número de grãos, o que pode se refletir em aumento considerável de produtividade. Esses resultados são importantes por mostrarem que mesmo a fração mais recalcitrante da MOS pode influenciar positivamente aspectos químicos e biológicos do solo, contribuindo com a melhoria do sistema de produção e também com maiores produtividades vegetais. / The soil organic matter (SOM) is composed of a complex and heterogeneous mixture of organic compounds, in which the humic substances (HS) are considered to be the most recalcitrant fraction. HS have great influence on chemical and biological soil properties, contributing as energy source for microorganisms and as nutrient reservoir for plants. Furthermore, HS can contribute significantly to the development and production of crop plants. Therefore, the objective of this study was to evaluate the activity and diversity of the soil bacterial community, nutrient availability and productivity of a wheat crop after application of increasing doses of HS. For this purpose, two experiments were performed and evaluated, one is an incubation essay with a sandy soil and the other a greenhouse experiment with wheat plants using two distinct tropical soils as substrates (sandy and clayey). Microbial activity was stimulated in both experiments, and this transient stimulus may have been due to a priming effect caused by the addition of HS. However, there was no change in the bacterial community structure which may be due to the fact that HS is a recalcitrant material and already present in the soil. Nevertheless, we found an increase in the availability of phosphorus, potassium, calcium and nitrogen, as well as in the CEC in both, sandy and clayey soils, showing that HS do improve chemical properties of tropical soils. Furthermore, we found a significant effect on wheat productivity related parameters. There was an increase of dry weight of roots and shoots, as well as increased weight and number of grains, which may be reflected in a significant increase in productivity. These results are important because they show that even the most recalcitrant SOM fraction can positively influence soil chemical and biological aspects, contributing to the improvement of the production system and also to higher plant productivity.

Resumo: O uso de bactéria como agente catalítico para a lixiviação de sulfetos minerais é largamente reconhecido hoje como uma metodologia interessante, sob o ponto de vista econômico e ambiental, para a recuperação de metais de minérios de baixo teor e minérios de sulfetos secundários. A principal bactéria envolvida neste processo é a Acidithiobacillus ferrooxidans, um microrganismo quimiolitotrófico e acidofílico que obtem energia através da oxidação do íon Fe2+, além das formas reduzidas de enxofre e sulfetos metálicos. Dentre os principais sulfetos metálicos encontrados nas reservas minerais de cobre, a calcopirita (CuFeS2) é a que mais se destaca por ser o mineral mais abundante e ao mesmo tempo mais refratário ao ataque químico e bacteriano. Dentro desse contexto há um grande interesse no desenvolvimento de alternativas para otimizar a solubilização desse sulfeto. Neste trabalho, foram investigados o efeito dos ácidos orgânicos e dos íons cloreto e na biolixiviação da calcopirita visando aumentar a solubilização de cobre desse sulfeto. Com relação ao estudo com os ácidos orgânicos (cítrico e oxálico) foi observado que a linhagem bacteriana A. ferrooxidans-LR foi inibida na presença do ácido oxálico em concentrações acima de 0,10 % m/v. Na presença de ácido cítrico não foi observado nenhuma inibição nas diversas concentrações utilizadas. Em função desses resultados o ácido cítrico foi o único a ser utilizado nos ensaios posteriores. O teste de solubilização das jarositas demonstrou que uma vez formada, ela não pode ser dissolvida pela adição de ácido cítrico. No entanto, este ácido mostrou-se eficiente para conter a formação destes precipitados. Os ensaios de biolixiviação na presença de ácido cítrico foram acompanhados por 60 dias através de medidas de pH, Eh, [Fe2+], [Fe3+] e [Cu]... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Acidithiobacillus ferrooxidans is a chemolithoautotrophic and acidophilic bacterium which obtain their energy through oxidation of the iron Fe+2 or sulfur reduced compounds including metal sulfides. This is the main species involved in the metals bioleaching process, an useful methodology to recovery metals from low-grade ores and secondary mineral sulfides. Chalcopyrite (CuFeS2) is one of the most abundant mineral of copper but at same time the most refractory, both to chemical and biological dissolution. So, it would be interesting to develop alternative technologies to improve copper solubilization from this sulfide. In the present study, it was investigated the effect of chlorine ions and organic acids in the chalcopyrite dissolution by bioleaching experiments in shake flask, following parameters such as pH, Eh, [Fe2+], [Fe3+] and [Cu]. Solid residues collected during and at end of assays were analyzed by X rays diffraction technique. The presence of Cl- ions (150 mmol L-1) and bacterium cells increased the degree of the chalcopyrite dissolution, comparing to abiotic controls and without Cl- ions. Two kinds of cell adaptation were also investigated regarding their capacity of copper extraction. Chlorine adapted cells showed better results than those adapted only to grow in chalcopyrite. Indeed, successive Cl- ions addition during experiment time course, at 10 e 20 mmol L-1, enhanced copper extraction in about 70% in comparison to that of 150 mmol L-1 in just one addition. The main new solid phase obtained during bioleaching experiments in inoculated flasks was covelllite, but jarosites were not produced in these conditions, which can be considered a promising result. The successive chlorine ion addition in bioleaching of chalcopyrite showed to be a potential procedure to improve copper extraction. Basically, the studies of organic acids (citric and oxalic)... (Complete abstract click electronic access below) / Orientador: Oswaldo Garcia Júnior / Coorientador: Denise Bevilaqua / Banca: Assis Vicente Bendetti / Banca: Ana Teresa Lombardi / Mestre

This diploma thesis focuses on validation of RP–HPLC method for determination of organic acids in fruit juices. The aim of this thesis was to determine suitability of the method for verification of the fruit juices authenticity based on analysis of organic acids. The theoretical part describes chemical composition of fruit and fruit juices and focuses on organic acids. It provides description of various methods of organic acids analysis with more detailed description of High Performance Liquid Chromatography and its validation. The experimental part focuses on optimalization and validation of the method. Samples of malic, citric, succinic and ascorbic acid were analysed. The optimalized method was validated and following performance parameters were determined: repeatability, linearity, limit of detection (LOD) limit of quantitation (LOQ). RP–HPLC method was applied to real samples of 100% fruit juices (apple, orange and grapefruit) and the authenticity parameters were verified.

This master thesis deals with the investigation of selected chemical and sensory characteristics of ciders, which were made from four selected apple varieties. The theoretical part describes the chemical composition of apples, cider, the technology of production and production in the world. The next section describes the analytical methods used to determine chemical characteristics not only in ciders but also in other alcoholic beverages. The experimental part focuses on the determination of chemical characteristics such as the content of organic acids, carbohydrates, total phenolic content, alcohol antioxidant activity and elemental composition. The purpose of the work was to find out how different varieties differ in chemical composition. The produced ciders were subjected to sensory analysis to evaluate the selected cider sensory parameters, which were in the natural state and with the addition of carbon dioxide. The results show that ciders of different varieties differ in chemical composition. Malic acid was the most cider's abundant of the organic acids in the range of 2759 – 4411 mg·l-1. Another acid represented was lactic acid in the range of 166,2 – 288,1 mg·l-1. The glucose content of each cider was determined between 845,3 – 1159,8 mg·l-1and fructose 32,6 – 406,7 mg·l-1. Potassium 944,29 – 1073,98 mg·l-1 was the most represented of all elements. The total phenolic content was determined to be in the range of 164,2 – 214,1 mg of GAE·l-1and the antioxidant activity of 0,192 – 0,318 mg·l-1. These differences in chemical composition were also reflected in sensory evaluation. According to the overall assessment, the best cider was made from the Granny Smith variety, which contained the most organic acids and carbohydrates. It has been found that by adding carbon dioxide, sensory parameters such as colour, taste and smell are altered.

The aim of this master’s thesis is perform basic analyses of samples ketchups. The theoretical part describes the basic characteristics of tomato, tomatoes processing and production of puree and ketchup. Then there are described analytical methods which were used for analysing the selected parameters in ketchups. The experimental part deals with the determination of pH, total solids, organic acids, saccharides, macroelements and lycopene in ketchups. Citrate and acetate were analysed by IC. The amount of acetate in ketchups was about 5 times greater than the amount of citrate. Glucose, fructose and sucrose were analysed by HPLC. Glucose and fructose were determined in all samples but sucrose not. The ICP-OES method was used to determine four elements. Magnesium was the least represented element and sodium was the most represented element in the analysis. The amount of sodium was recalculated on the amount of salt. Lycopene was analysed by UV-VIS spectrometry. Its amount in ketchups is influenced by the variety of used tomatoes and plenty of other factors.

The only treatment for coeliac disease, a common autoimmune disorder, is life-long adherence to a gluten-free diet. However, the replacement of wheat gluten, a key structural and functional component in bread, poses a major technological challenge for food scientists. The use of non-wheat cereal proteins, as alternatives to gluten, shows much promise in gluten-free bread making. Literature has shown that when zein, the maize prolamin protein, is subjected to wet heat above its glass transition temperature (Tg), the protein becomes viscoelastic, rubbery and dough-like. Gluten-like fibrils are visible, which form complex protein networks similar to those found in wheat dough. The resulting zein dough has viscoelastic characteristics and can be successfully used with hydrocolloids to produce gluten-free bread. This project examined the influence of wet heat treatment and dilute organic acids (lactic acid and acetic acid) on the dough-making quality of non-wheat cereal proteins, such as kafirin and zein. Zein was the only non-wheat cereal protein to show any physical change when it was subjected to wet heat treatments, forming a dough-like substance. Acidification of the zein dough prepared at 40°C with concentrations of 0.7, 1.3 and 5.4% (v/v) organic acid in distilled water solutions, showed that the higher the concentration of acid used, the greater its effect on the dough's rheological properties. Tensile tests using a Keifer rig on zein dough showed that as the concentration of organic acid was increased from 0.7 to 1.3 and to 5.4% (v/v) the dough become softer and increasingly more extensible. The dough also exhibited less resistance to extension and reduced elasticity. CLSM revealed that the zein doughs contained a protein network, made up of fine protein fibrils, which became smoother and more homogenous as the concentration of acid was increased. Although SDS-PAGE revealed that no oligomerization took place with acid addition, iv FTIR showed that zein dough prepared with distilled water at 40°C had elevated levels of β-sheets. When organic acids were added in increasing levels, corresponding increases in the quantities of α-helices in the protein were observed. Alveography showed that zein-based doughs prepared with dilute organic acids retained gases well and that the concentration of dilute organic acids influenced dough distensibility (biaxial extensibility) and stability (the ability of the dough to retain gas). Low concentration of acids (0.7 and 1.3%) increased dough stability to levels similar to that of strong wheat flour, 103 mm H2O, but higher concentrations of acids (5.4%) led to a marked reduction in dough stability. Thus, by increasing zein dough functionality to such an extent, the apparent usefulness of the doughs and their ability to retain gases produced during fermentation is reduced. Simple distensibility tests on zein doughs showed that added organic acids promoted ‘clumping’ of the fine protein fibrils in the dough network into pronounced fibres. This would account for the decreased dough stability when high levels (5.4%) of organic acids were used. Baking trials with zein doughs were not successful as adequate leavening was impossible without an acid-tolerant leavening agent. It is believed that dilute organic acids influence the rheological properties of zein dough by creating a positively charged environment, in which the protein is partially solubilized. The higher the level of organic acid used, the greater the positive net charge and the more pronounced the effect on the protein network structure. Organic acids could also improve fluidity of the zein dough by acting as plasticizers. From this work it can be seen that although a protein network is present in all zein-based doughs, the ability of this network to retain gases is dependant on the level of organic acids present. The functional properties of zein-doughs made with low levels of organic acids (0.7 and 1.3%) shows potential in the production of gluten-free bread for individuals suffering from coeliac disease. / Dissertation (MSc)--University of Pretoria, 2013. / gm2014 / Food Science / unrestricted

Une triple attente socio-économique dans les domaines du développement durable (réduction des matières synthétiques non biodégradables), des solutions naturelles de conservation des aliments (tendance du « clean label » par la protection des denrées par des emballages actifs et intelligents évitant des additifs à outrance dans les aliments) et de la sécurité alimentaire (sécurité microbiologique et traçabilité) est à l’origine du développement de nouveaux matériaux à la fois biodégradables, comestibles et fonctionnalisés. Cette recherche commencée quelques décennies plus tôt est freinée par un mode de production difficilement industrialisable (voie solvant). Cependant, depuis quelques années des procédés applicables à l’échelle industrielle sont développées (voie fondue/extrusion). Dans le travail présenté ici, la technologie d’extrusion bivis a été appliquée avec succès sur différentes matières premières protéiques : la caséine acide, la caséine présure et le caséinate de sodium. Extraites toutes trois du lait de vache, ces caséines montrent des caractéristiques différentes qui affectent les propriétés du matériau (mécaniques, sensibilité aux molécules d’eau). La fonctionnalisation de la matrice par l’ajout d’acides organiques offre un potentiel antimicrobien intéressant contre Escherichia coli. Une complexation supplémentaire du matériau par incorporation de molécules hydrophobes telles que des cires (cires d’abeille, de candelilla et de carnauba) permet d’élargir une fois de plus l’éventail des propriétés disponibles pour ces matériaux composites, comme l’amélioration de la propriété barrière à la vapeur d’eau apportée par la cire d’abeille. La sensibilité aux molécules d’eau de ce type de matériau étant un critère à considérer à chaque étape de développement et de compréhension des interactions inter-ingrédients (protéine, plastifiant, cires, composés antimicrobiens). Ce manuscrit expose le potentiel de développement de matériaux à base de caséine, biodégradables, comestibles et antimicrobiens, qu’il s’agit d’appliquer en emballage agroalimentaire tout comme dans bien d’autres secteurs / Development of innovative biodegradable, edible and functionalized material comes from a triple socio-economic expectation in the field of sustainable development (decrease in synthetic non-biodegradable polymers), of natural solutions for food preservation (trend of “clean label” by food protection through active and smart packaging to avoid over-use of food additives) and of food safety (microbiological safety and traceability). Development in that field, started few decades ago is slowed down by production process (wet process), which is not an easy scale up process. However, a few years ago industrial process technique as extrusion started developing. In the present work, the twin-screw extrusion process was successfully applied to produce polymer based on protein raw material: acid casein, rennet casein and sodium caseinate. Extracted from caw milk, these three caseins own different characteristics, which affect material properties (mechanical, water sensitive properties). Matrix functionalization through organic acid addition bring an interesting antimicrobial response against Escherichia coli. Blending hydrophobic molecules as waxes (beeswax, candelilla wax and carnauba wax) creates a complex composite material which increases the range of available properties as improved water vapor barrier allowed by beeswax addition. Water sensitive properties are key points to consider at each step of material development and to understand relationships between the different ingredients (protein, plasticizer, waxes, antimicrobial agents). This manuscript shows the feasibility in the development of casein based material as biodegradable, edible and antimicrobial material, to apply and use in the food packaging industry or other industries