Three systems were compared in the first case study: (1). pre-dissolved β-carotene nanoemulsion (d< 200nm); (2). corn oil emulsion (d< 200nm) with β-carotene crystals being added before digestion; (3). phosphate buffer saline with β-carotene being added before digestion. Oil-in-water nanoemulsions were formed by high-pressure homogenization using Tween 20 as emulsifier and corn oil as carrier oil and then they were subjected to a simulated mouth, stomach and small intestine digestion. The rate and extent of free fatty acid production in small intestine decreased in the order (2)>(1)>(3); whereas the β-carotene bioaccessibility decreased in the order (1)>>(2)>(3). In system (3), even without any fat content, there is still noticeable consumption of NaOH, which is due to the ester bonds existing in the non-ionic surfactant (Tween 20). In the second case study, we developed two comparing groups by differentiating their oil concentration (20%, 4% respectively). The bioaccessibility of the high fat group is only half of the low fat group due to the insufficient digestion of fat in the former group. In the third case study, the bioaccessibility of nobiletin with different physical states (crystalized vs solubilized) and in different delivery system (conventional emulsion vs nanoemulsion) was compared. Not like β-carotene, the bioaccessibility of nobiletin as crystals in slightly lower than it is as solubilized state. Meanwhile, in conventional emulsion, the bioaccessibility is slightly lower than in nanoemulsion. This study provides important information for developing effective delivery systems for lipophilic bioactive components in food and beverage applications.

No description available.

The functional ingredient curcumin has a variety of biological and pharmacological actions, such as anti-tumor, anti-inflammatory, anti-virus, anti-oxidant, and anti-HIV properties coupled with low toxicity. However, curcumin possesses low bioavailability due to its poor solubility in water. The purpose of this study was to investigate the impact of different lipid-based formulations of curcumin on in vitro solubilization and bioaccessibility. Oils representing LCT, MCT, LCT:SCT mix and SCT were used to prepare O/W (nano)emulsions with droplet sizes as low as 174 nm. An in vitro digestion model simulating the small intestine milieu in the fasted and fed state was used to characterize rate, extent, and particle size associated with emulsion digestion. Rate and extent were oil dependent, but not particle size. SCT emulsions digested at the fastest initial rate, but MCT emulsions were digested to the largest extent. Bioaccessibility, a precursor to eventual bioavailability, was determined after digestion using a curcumin:lipid content dependent and independent method. MCT produced the highest bioaccessibility of curcumin for each method. Nanoemulsion digestion and bioaccessibility results were compared to conventional emulsions because an appropriate comparison was needed to determine the merits of the nanoemulsion delivery system. There was no significant difference in particle size and bioaccessibility between the conventional and nanoemulsions.

No description available.

No description available.

Lead (Pb), a trace metal notorious for its impacts on human health, has achieved worldwide environmental dispersal resulting from centuries of use by human society. The toxicity of Pb is governed largely by its mineral form, which is in turn controlled by pH, localized reactivity and soil processes that differ according to soil type, location and Pb source. Given the context of these localized dependencies, or site specificity, efforts to predict Pb toxicity and refine sustainable remediation techniques are most useful when Pb behavior is constrained and predicted within environments with homogeneous conditions, such as a single soil. I evaluated and predicted the behavior of Pb, a typical anthropogenic contaminant, within a single soil using bioaccessibility testing and predictive geospatial modeling to assess potential impacts and refine sustainable remediation methods. To test the hypothesis that Pb speciation is influenced by competitive sorption processes in soils, I investigated changes in mobility and speciation of Pb upon addition of amendments at multiple scales using flow-through column experiments, soil characterization and synchrotron-based x-ray techniques. Kriging and cokriging maps provided a successful estimation of background and total Pb, the latter incorporating housing age as a secondary variable to increase model accuracy, though efforts to automate detection of background Pb were complicated by approximation of building extents, and overall heterogeneity of soil Pb concentration gives high error. Acute Pb heterogeneity is observed at the scale of a single site among near-structure samples. At the city-scale, determination of bioaccessibility revealed that bioaccessible and total Pb are well-correlated, to the extent that bioaccessibility may be predicted for the soil underlying Burlington, VT; this information, combined with predictive blood lead level modeling and the CDC's recent establishment of 5 μg kg-1 as a threshold for blood lead toxicity, enabled the establishment of a site-specific revised soil Pb limit of 360 mg kg-1, lower than the EPA's general soil Pb threshold of 400 mg kg-1. Characterization of leached and unleached soil using scanning electron microscope energy dispersive spectroscopy (SEM-EDS) and microfocused x-ray techniques provided a first look at Pb paint species using synchrotron technologies. Pb was present within paint chips as hydrocerussite, but appeared to weather to anglesite over time. Pb also seemed to act as cation bridge, attracting clay minerals electrostatically and becoming incorporated into heterogeneous soil aggregates. Accessory paint elements are identified in soil and within paint chips and may further complicate these systems. Column experiments, at acidic pH, yielded little evidence of Pb mobility change in response to modification of competitive sorbents. Kinetics of Pb release were driven by pH, with Pb solubilizing at pH of ˜4.9 as column soil acidifies. This work provides evidence for changes in Pb speciation over time in urban soils impacted by Pb paint, and presents a framework for predictive risk analysis at a local site using experimental and modeling tools. Multiscale observations and analytical results can be used in future efforts to model and refine sustainable remediation solutions within a site-specific context.

Selon la FAO, 2 milliards de personnes souffrent de la « faim cachée » qui correspond aux carences en micronutriments incluant la carence en vitamine A, principale cause de cécité dans le monde. Par ailleurs, une alimentation excédentaire est source de stress oxydant pour le corps, facteur de risque de nombreuses maladies non transmissibles comme le diabète et les maladies cardiovasculaires. Contenus dans les produits végétaux, certains caroténoïdes représentent une source indirecte de vitamine A et pourraient participer aux effets bénéfiques de la consommation de fruits et légumes via des propriétés antioxydantes. Dans cette thèse, le comportement in vitro des caroténoïdes et rétinoïdes pendant la digestion a été étudié, depuis leur libération de la matrice alimentaire jusqu'à leurs interactions avec les cellules intestinales. Mes recherches s'articulent autour de la micellisation : processus clé de l'absorption des caroténoïdes et rétinoïdes. Dans un premier temps, la stabilité et la bioaccessibilité en digestion in vitro de ces composés purs ont été comparées à celles de leurs homologues issus d'un jus de carotte, d'épinards crus et cuits et d'une farine fortifiée. Dans un deuxième temps, un nouveau modèle d'oxydation de nano-émulsions intestinales à base de sels biliaires (SB) a été développé. Les relations entre structure des micelles mixtes, réactivité à l'oxydation et protection par des antioxydants ont été étudiées grâce notamment au suivi de la dégradation des acides gras. Enfin, des expériences préliminaires ont été menées sur la réactivité enzymatique de cellules coliques (Caco-2) à divers oxydants et aux micelles mixtes. Pendant la digestion in vitro, le β-carotène et palmitate de rétinyl purs étaient particulièrement instables contrairement à la lutéine et à l'acétate de rétinyl. De plus, la matrice alimentaire protège ces composés et favorise leur bioaccessibilité surtout lorsqu'elle est broyée ou cuite. En effet, les prétraitements ont un impact conséquent sur la libération des caroténoïdes et doivent être considérés comme des moyens sérieux pour optimiser les apports. Les nano-émulsions intestinales mises au point se composaient de micelles mixtes sphériques ou cylindriques, ces dernières étant les moins résistantes à l'oxydation. En effet, la distribution des molécules de SB doit être différente selon la morphologie de la micelle, impactant ainsi leur réactivité. Dans nos conditions expérimentales, l'AAPH fut le seul oxydant efficace. L'α-tocophérol et la lutéine ont significativement ralenti la dégradation des acides gras contrairement au β-carotène. Leur place au sein de la micelle (cœur ou bordure) pourrait expliquer ces observations. Enfin, aucun des oxydants testés n'a significativement modifié l'activité catalase des cellules Caco-2. En revanche, la mise en contact avec les micelles à base de SB ont significativement diminué l'activité des 3 enzymes suivies. L'effet était positivement corrélé à la concentration en SB dont la conjugaison fut un élément déterminant. Finalement, le β-carotène, la lutéine, et l'acétate de rétinyl présents dans ces micelles ont en partie rétabli l'activité de la catalase contrairement au rétinol, palmitate de rétinyl et à l'α-tocophérol. / According to the FAO, two billions of people suffer from the « hidden hunger » which corresponds to micronutrient deficiencies and includes the vitamin A deficiency, principal cause of blindness throughout the world. Besides, an excessive food consumption entails an oxidative stress for the organism which increases the risk to develop non communicable diseases such as diabetes and cardiovascular diseases. Present in numerous fruits and vegetables, some carotenoids are an indirect source of vitamin A and could also contribute to the health benefits of the consumption of fruits and vegetables via antioxidant properties. In this thesis, in vitro behaviour of carotenoids and retinoids during in vitro digestion (IVD) has been studied, from their release from dietary matrices to their interactions with intestinal cells. My research is structured around micellisation: key process of carotenoid and retinoid absorption. First, stability and bioaccessibility during IVD of these pure compounds have been compared with those of their homologues from carrot juice, raw and cooked spinach and fortified flour. Second, a new model of oxidation of intestinal bile salt (BS)-based nanoemulsions has been developed. Relations between mixed micelles structure, reactivity to oxidation and protection by antioxidants have been studied using fatty acid degradation monitoring. Finally, preliminary experiment were carried out on enzymatic reactivity of colon cells (Caco-2) to various oxidants and mixed micelles. During IVD, pure β-carotene and retinyl palmitate were particularly unstable conversely with lutein and retinyl acetate. Moreover, the dietary matrix protected these compounds and favoured their bioaccessibility especially when it was grounded or cooked. Indeed, pre-treatment have a significant impact on carotenoid release and should be considered as serious means to optimize intake. Developed intestinal nanoemulsions constituted of spherical or cylindrical micelles, the latter being less resistant to oxidation. Distribution of BS molecules is likely to differ according to the micelle morphology, thereby influencing their reactivity. In our experimental conditions, AAPH only was efficient as oxidant. Lutein and α-tocopherol significantly slowed fatty acid degradation, conversely with β-carotene. Their location within the micelle (core or border) could explain these observations. Besides, none of the tested oxidant significantly modified the catalase activity of Caco-2 cells. However, the contact with BS-based nanoemulsions significantly decreased the activity of the three tested enzymes. This effect was positively correlated with BS concentration whose conjugation revealed determining. Finally, β-carotene, lutein and retinyl acetate in micelles partly re-established catalase activity, conversely with retinol, retinyl palmitate and α-tocopherol. To conclude, IVD is an easy tool which allows independent comparisons of several parameters on micronutrient behaviour during digestion. Furthermore, the confrontation of different matrices may help to develop relevant strategies against vitamin A deficiency. Proposed nanoemulsions displayed various physical and chemical characteristics, thereby influencing their reactivity to oxidation. The antioxidant capacity of lutein and α-tocopherol could be observed in this new model. Lastly, the preliminary results on Caco-2 cells revealed some interesting interactions between micellised BS and antioxidant enzymes. Numerous questions arose that could not be addressed in this work but open perspectives for the future.

Dans un contexte où les carences en micronutriments constituent un problème majeur de santé publique touchant particulièrement les jeunes enfants, l'étude de la rétention et de la biodisponibilité du fer et du zinc dans les plats les plus fréquemment consommés peut constituer une stratégie de lutte contre les carences en ces minéraux. Une enquête de consommation alimentaire par pesées auprès de 630 enfants de 6 à 36 mois au Burkina Faso a permis de dégager les principales caractéristiques de l'alimentation de complément des jeunes enfants. Les résultats mettent en évidence une couverture des apports recommandés en fer et en zinc très faible, des apports élevés en fibres et en phytates. Le jour de l'enquête, plus de 90% des enfants avaient consommé du mil, du sorgho ou du maïs, essentiellement sous forme de tô, une pâte très consistante, de bouillie ou de galettes. Des suivis de préparation de ces plats dans les ménages ont permis d'identifier les principales opérations unitaires susceptibles d'avoir un effet sur les teneurs en fer et en zinc et leur biodisponibilité. Le décorticage traditionnel, manuel ou mécanique, entraine d'importantes pertes en fer (50% dans le mil pour 10% de perte de MS) et en zinc (23% dans le sorgho pour 7% de perte de MS). Les variétés biofortifiées présentent un comportement similaire, mais permettent tout de même une amélioration significative du rapport molaire phytate/zinc. La mouture, lorsqu'elle est réalisée à l'aide d'un moulin à meules, entraine une contamination en fer, allant jusqu'à tripler la teneur en fer initiale des grains. Mais la bioaccessibilité de ce fer est extrêmement faible. L'acceptabilité des variétés de mil biofortifiées, testées sur différents plats, reste inférieure à celle de la variété locale. L'amélioration des procédés combinée à l'utilisation de variétés biofortifiées pourrait être promue afin de contribuer à la lutte contre les carences en fer et zinc. / In contexts where micronutrient deficiencies are a major public health concern, the improvement of the retention and bioavailability of iron and zinc in dishes frequently consumed by young children could be part of a food-based strategy to combat these deficiencies. A food consumption survey using weighing records was carried out on 630 children from 6 to 36 months in Burkina Faso. This permitted to highlight the main characteristics of the children diet. Iron and zinc intakes were far below the recommended intakes. High fibre and phytate intakes were also observed. More than 90% of the young children consumed millet, sorghum or maize in the day of the survey. A detailed monitoring of the traditional processing of the cereal dishes permitted the identification of the main unit operations that could have an effect on iron and zinc content and bioavailability. Important losses in iron content (50% in millet for 10% DM loss) and zinc (23% in sorghum for 7% DM loss) were observed after traditional dehulling, either manual or mechanical. Biofortified varieties showed similar behaviour but their phytate/zinc molar ratio was still improved. During milling in local mill with grindstones, iron contamination occurred, and tripled the initial iron content. But the bioaccessibility of this contaminant iron was very low. The acceptability of the biofortified varieties of millet, tested on various dishes, was lower than that of the local variety. The improvement of the processing methods combined with the use of biofortified varieties could be advantageously promoted to contribute to alleviate iron and zinc deficiencies.

Les caroténoïdes sont une famille de molécules lipidiques que l’on trouve en particulier dans les végétaux, et qui ont pour caractéristique visuelle d’être colorés, du jaune au rouge. Ils ont été identifiés comme nutritionnellement actifs par des études épidémiologiques. Afin de pouvoir jouer un rôle dans l’organisme les caroténoïdes doivent être absorbés. Pour ce faire ils doivent être libérés de la matrice alimentaire afin de passer après plusieurs étapes dans la circulation sanguine. Or les caroténoïdes des végétaux sont connus pour être peu biodisponible. Cette biodisponibilité augmente après transformation. L’objectif de ce travail est donc de comprendre l’effet des procédés de fabrication sur la bioaccessibilité, en développant un outil simple permettant aux industriels de l’évaluer facilement. Le lycopène de la tomate a été choisi comme molécule d’intérêt. Dans un premier temps, une méthode d’étude de la diffusion du lycopène entre la matrice végétale et la phase lipidique du bolus alimentaire est mise en place. En utilisant cette méthode avec un large extrait d’huile, seulement 31%±1% du lycopène à put être extrait du jus de tomate vers la phase huile. Avec des ratio faible (entre 0.11 et 1) huile/tomate, l’extraction du lycopène est limitée par la saturation de l’huile. La diffusion du lycopène ne varie pas significativement avec le pH mais va augmenter lorsque la température varie de 10 °C à 37 °C. A partir de ces résultats sont calculés les facteurs de partition du lycopène dans l’huile ainsi que sa diffusivité.Dans un deuxième temps, des échantillons contrastés à base de tomates sont réalisés par l’utilisation des procédés Hot Break (HB) et Cold Break (CB) afin de vérifier l’impact des procédés de transformation sur les propriétés de diffusion du lycopène. Enfin, le test de diffusion a été appliqué à différentes matrices, produits commerciaux, ou frais transformés en laboratoire afin de vérifier son aptitude à les classifier. Ce travail à permis de construire les bases d’un modèle de diffusion du lycopène prenant en compte la première étape de son ingestion, la diffusion vers la phase lipidique. Les résultats obtenus pourront être confrontés à des résultats sur d’autre matrice et ainsi permettre l’élaboration d’un modèle de digestion tenant compte des différents paramètres mis en avant au cours de cette étude / Carotenoids are natural fat-soluble pigments synthesized by plants, and especially found in relatively high amounts in numerous fruits and vegetables and which have the visual characteristic of being colored from yellow to red.These compounds were identified as being beneficial to health by epidemiological studies.In order to play a role in body carotenoids have to be absorbed. They must be released from the matrix to pass in the lipid phase of the bolus. Or plant carotenoids are known to have a low bioavailability. The bioavailability increases after transformation. The objective of this work is to understand the effect of manufacturing processes on the bioavailability, developing a simple tool allowing manufacturers to easily evaluate Lycopene tomato was selected as molecule of interest. Therefore we designed a model to evaluate these parameters which can modify carotenoids diffusion. Using this model, even with a large excess of oil, only 31%±1% of lycopene could be extracted from tomato juice to the oil phase. At low (between 0,11 and 1) oil/tomato ratio, extraction of lycopene was limited by saturation of the oil phase. The lycopene diffusion did not vary significantly with pH but it doubled when temperature rose from 10 °C to 37 °C. From these results are calculated factors partition of lycopene in oil and its diffusivity. Secondly, contrasting tomato samples were carried out by using the two industrials methods Hot Break (HB) and Cold Break (CB) in order to verify the effect of processing methods on the diffusion properties of lycopene. Finally, the diffusion test was applied to different matrix, commercial products, or fresh products processed in the laboratory to verify its ability to classifier them. This work gave stable and repeatable results and may be used for a reliable and quick evaluation of the impact of process on food matrix, which could enhance the carotenoid bioavailability. It is also a powerful tool to study the physico-chemical parameters that may affect this bioaccessibility. Results obtained may be used to develop a new model of digestion witch used various parameters highlighted during this study

Fertilizantes minerais derivados de rochas fosfáticas podem ser uma fonte de contaminantes, como As, Cd, Cr, Pb e Hg. Além disso, resíduos de indústrias metalúrgicas e químicas podem ser adicionados à composição de fertilizantes para fornecer micronutrientes, atuando como uma fonte adicional de contaminantes. Desta forma, o controle de qualidade de fertilizantes e matérias-primas é importante para evitar danos ao meio ambiente e garantir uma produção segura de alimentos. Neste trabalho, procedimentos de digestão assistida por radiação micro-ondas de um fertilizante mineral formulado e uma mistura de micronutrientes foram desenvolvidos para a determinação simultânea de Al, As, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb e Zn por ICP OES, avaliando doze misturas ácidas contendo HNO3, HCl, H3PO4, HF e H3BO3. A PCA foi aplicada para auxiliar a escolha de três procedimentos de digestão que exibiram os resultados com maior exatidão. O protocolo de extração sequencial do BCR foi aplicado para investigar a mobilidade e a bioacessibilidade dos elementos. As e Cd foram extraídos principalmente na primeira etapa, portanto estão fracamente ligados à matriz e, consequentemente, estão mais móveis e bioacessíveis. O Cr permaneceu quase que completamente na fração residual. O Pb apresentou maior mobilidade e bioacessibilidade na mistura de micronutrientes do que no fertilizante mineral formulado, possivelmente, devido a precipitação de Pb3(PO4)2, causado pela alta concentração de P no fertilizante. Os nutrientes (P, Ca, Mg, Cu, Mn e Zn) apresentaram boa bioacessibilidade, exceto Fe, que permaneceu quase totalmente na fração residual. Além disso, análises por DRX e MEV-EDS foram empregadas para caracterizar os resíduos sólidos das extrações, mostrando que os elementos podem ser cobertos por estruturas cristalinas (quartzo), que inibem a sua lixiviação e os tornam menos móveis e bioacessíveis. Um sistema de extração em fluxo foi proposto para avaliar a mobilidade e a bioacessibilidade de As, Cd, Cr e Pb em fertilizantes, que foi mais eficiente que os procedimentos em batelada, pois o sistema em fluxo simula a constante lixiviação que ocorre no solo, com a infiltração das águas de chuva ou irrigação das plantações. Além disso, essas análises foram realizadas no modo transiente do ICP OES, que permitiu avaliar a cinética de extração dos elementos. O procedimento foi empregado para misturas de fertilizante com solo, onde foram observados sinais que demoravam a retornar a linha base, demonstrando a interação dos elementos com a matriz do solo. Um estudo de especiação por XANES também foi realizado e possibilitou a identificação das espécies As(V), Fe2-xCrxO3 e PbCl2 no fertilizante e na mistura de micronutrientes. Ensaios realizados com brotos de milho foram realizados para avaliar a translocação de As, Cd, Cr e Pb. Além disso, a partir das análises de especiação de As por HPLC-ICP-MS, foi observado que exsudatos promoveram a redução do As(V) para As(III), sendo esta a espécie absorvida e translocada pela planta. / Mineral fertilizers derived from phosphate rocks can be a source of contaminants, such as As, Cd, Cr, Pb and Hg. In addition, metallurgical and chemical industry residues can be added to the fertilizer composition to provide micronutrients, acting as an additional source of contaminants. In this way, the quality control of fertilizers and raw materials is important to avoid damages to the environment and ensure a safe food production. In this work, microwave-assisted digestion procedures of a formulated mineral fertilizer and a mixture of micronutrients were developed for simultaneous determination of Al, As, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb and Zn by ICP OES, evaluating twelve acidic mixtures containing HNO3, HCl, H3PO4, HF and H3BO3. PCA was applied to assist in the choice of three digestion procedures that exhibited the more accurate results more. The BCR sequential extraction protocol was applied to investigate the elements mobility and bioaccessibility. As and Cd were extracted mainly in the first step, thus they are weakly bound to the matrix and, consequently, are more mobile and bioaccessible. The Cr remained almost completely in the residual fraction. Pb presented higher mobility and bioaccessibility in the mixture of micronutrients than in the formulated mineral fertilizer, possibly due to the precipitation of Pb3(PO4)2 caused by the high concentration of P in the fertilizer. The nutrients (P, Ca, Mg, Cu, Mn and Zn) presented good bioaccessibility, except Fe, which remained almost totally in the residual fraction. In addition, XRD and SEM-EDS analyzes were employed to characterize the solid residue from extractions, showing that the elements can be covered by crystalline structures (quartz), which inhibit their leaching and make them less mobile and bioaccessible. A flow extraction system was proposed to evaluate the mobility and bioaccessibility of As, Cd, Cr and Pb in fertilizers, which was more efficient than batch procedures, because the flow system simulates the constant leaching occurring in soil, with infiltration of rainwater or irrigation of plantations. In addition, these analyses were performed in the transient mode of ICP OES, which allowed evaluating the kinetics of elements extraction. The procedure was applied to mixtures of fertilizer with soil, where a slow return to baseline of signal was observed, demonstrating the interaction of the elements with the soil matrix. XANES speciation study was also carried and allowed the identification of the species As(V), Fe2-xCrxO3 and PbCl2 in the fertilizer and mixture of micronutrients samples. Bioassays performed with maize sprouts were carried out to evaluate the translocation of As, Cd, Cr and Pb. In addition, from As speciation analysis by HPLC-ICP-MS, it was observed that exudates promoted the reduction of As (V) to As (III), being this the species absorbed and translocated by the plant.