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Aim: The prevalence of dental erosion is still increasing. A possible preventive approach might be rinsing with edible oils to improve the protective properties of the pellicle layer. This was tested in the present in situ study using safflower oil. Methods: Pellicle formation was carried out in situ on bovine enamel slabs fixed buccally to individual upper jaw splints (6 subjects). After 1 min of pellicle formation subjects rinsed with safflower oil for 10 min, subsequently the samples were exposed in the oral cavity for another 19 min. Enamel slabs without oral exposure and slabs exposed to the oral cavity for 30 min without any rinse served as controls. After pellicle formation in situ, slabs were incubated in HCl (pH 2; 2.3; 3) for 120 s, and kinetics of calcium and phosphate release were measured photometrically (arsenazo III, malachite green). Furthermore, the ultrastructure of the pellicles was evaluated by transmission electron microscopy (TEM). Results: Pellicle alone reduced erosive calcium and phosphate release significantly at all pH values. Pellicle modification by safflower oil resulted in an enhanced calcium loss at all pH values and caused an enhanced phosphate loss at pH 2.3. TEM indicated scattered accumulation of lipid micelles and irregular vesicle-like structures attached to the oil-treated pellicle layer. Acid etching affected the ultrastructure of the pellicle irrespective of oil rinsing. Conclusion: The protective properties of the pellicle layer against extensive erosive attacks are limited and mainly determined by pH. The protective effects are modified and reduced by rinses with safflower oil. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Aim: The prevalence of dental erosion is still increasing. A possible preventive approach might be rinsing with edible oils to improve the protective properties of the pellicle layer. This was tested in the present in situ study using safflower oil. Methods: Pellicle formation was carried out in situ on bovine enamel slabs fixed buccally to individual upper jaw splints (6 subjects). After 1 min of pellicle formation subjects rinsed with safflower oil for 10 min, subsequently the samples were exposed in the oral cavity for another 19 min. Enamel slabs without oral exposure and slabs exposed to the oral cavity for 30 min without any rinse served as controls. After pellicle formation in situ, slabs were incubated in HCl (pH 2; 2.3; 3) for 120 s, and kinetics of calcium and phosphate release were measured photometrically (arsenazo III, malachite green). Furthermore, the ultrastructure of the pellicles was evaluated by transmission electron microscopy (TEM). Results: Pellicle alone reduced erosive calcium and phosphate release significantly at all pH values. Pellicle modification by safflower oil resulted in an enhanced calcium loss at all pH values and caused an enhanced phosphate loss at pH 2.3. TEM indicated scattered accumulation of lipid micelles and irregular vesicle-like structures attached to the oil-treated pellicle layer. Acid etching affected the ultrastructure of the pellicle irrespective of oil rinsing. Conclusion: The protective properties of the pellicle layer against extensive erosive attacks are limited and mainly determined by pH. The protective effects are modified and reduced by rinses with safflower oil. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Si les lipides contribuent à la valeur nutritionnelle et sensorielle de nombreux aliments, ils sont particulièrement sensibles aux réactions d'oxydation. Les principaux mécanismes mis en jeu lors de l'oxydation des acides gras insaturés sont relativement bien connus. En revanche, il est aujourd'hui quasiment impossible de prédire l'avancement des réactions et souvent nécessaire de recommencer une nouvelle étude de stabilité oxydative pour tout nouveau couple produit alimentaire / procédé de transformation. L'objectif de la thèse est donc de construire un modèle mécanistique couplé à un modèle de transfert de l'oxygène dans le but de prédire l'avancement des réactions d'oxydation dans un milieu lipidique continu et dans des conditions expérimentales définies et contrôlées (température, oxygénation, composition en acides gras, composition en antioxydants). Pour cela, un schéma réactionnel visant à détailler l'ensemble des réactions impliquées dans le phénomène d'auto-oxydation des lipides a été proposé puis un modèle stoechio-cinétique a été construit à partir des valeurs des paramètres cinétiques issues de la littérature. La réactivité des acides gras insaturés présents dans trois huiles végétales d'usage courant (colza, tournesol, tournesol oléique), purifiées de leurs antioxydants naturels, a été étudiée entre 80 et 180°C, en suivant différents marqueurs d'oxydation (diènes conjugués, hydroperoxydes, aldéhydes, polymères). Comme attendu, les cinétiques d'oxydation se sont avérées dépendantes de la composition des huiles en acides gras, de la température et des conditions d'oxygénation. L'ajout d'antioxydant(s) a confirmé l'effet protecteur de l'α-tocophérol, qui n'a pas été amélioré par un enrichissement en acide chlorogénique, acide phénolique naturellement présent dans les graines de tournesol. Les résultats obtenus ont été utilisés pour valider le modèle développé, dont les prédictions permettent de reproduire les tendances expérimentales. Deux limitations ont été mises en évidence au cours de cette phase de validation dont la première concerne la description fiable et précise du mécanisme d'oxygénation du milieu, qu'il sera nécessaire de mesurer dans une huile à haute température pour valider le modèle d'oxydation. Par ailleurs, compte tenu du nombre important de réactions prises en compte, il sera indispensable de disposer d'un jeu de données expérimentales plus important, pouvant inclure des intermédiaires radicalaires. Pour cela, les potentialités de la résonance paramagnétique électronique ont été étudiées au cours de ce travail, à la fois pour suivre les radicaux lipidiques et pour accéder à des paramètres cinétiques pour des réactions radicalaires, peu disponibles dans la littérature. / If lipids contribute to nutritional and sensorial properties of many foodstuf, they are particularly sensitive to oxidation reactions. The main mechanisms involved in the oxidation of unsaturated fatty acids are already well-known. However, it is almost impossible to predict the progress of oxidative reactions and often necessary to develop new studies of oxidative stability for each new food product / processing. The aim of this study is to develop a mechanistic model coupled to oxygen transfer in order to predict the evolution of oxidation reactions in a bulk lipid system and in defined and controlled experimental conditions (temperature, oxygenation, fatty acids' composition, antioxidants' composition). Thus, a reaction scheme detailing all the reactions involved in the oxidation phenomenon was proposed and a stoichio-kinetic model was built on the basis of conservation equations and kinetic parameters available in literature. The reactivity of unsaturated fatty acids contained in three usual edible oils (rapeseed, sunflower, high oleic sunflower), previously stripped of their natural antioxidants, was studied between 80 and 180 °C, following several oxidation markers (conjugated dienes, hydroperoxides, aldehydes, polymers). As expected, oxidation kinetics depended on fatty acids' composition of oils, on temperature and on oxygen availability. The addition of antioxidant(s) confirmed the protective effect of α-tocopherol, which was not improved by the enrichment in chlorogenic acid, a phenolic acid naturally occurring in sunflower seeds. The experimental data were used to validate the model which predictions reproduce experimental tendencies. Two limitations were identified during model validation. The first is the accurate description of the oxygenation mechanism of the medium which need to be measured in oil at high temperatures. Moreover, given the large number of reactions taken into account, it is essential to have a set of more important experimental data which include radical intermediates. For this, the potential of electron spin resonance spectroscopy was evaluated in this in order to follow lipid radical species and access to kinetic parameters of radical reactions, few available in literature.

Made available in DSpace on 2015-05-14T13:21:30Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1275793 bytes, checksum: 6f184080723f11f294f29a4ddad08f39 (MD5) Previous issue date: 2013-08-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this study a flow-batch analyzer (FBA) was utilized and its performance was evaluated for the determination of Fe(III) in edible without external pretreatment. The FBA method uses the reaction between Fe(III) and thiocyanate in organic medium. The formed red complex was monitored by employing a light emitting diode (LED, λmax = 520 nm) and a phototransistor linked to the mixing chamber by optical fibers. All standard solutions were prepared in-line and all analytical processes were carried out by simply changing the operational parameters in FBA control software. Comparing with the reference method, no statistically significant differences were observed when applying the paired t-test at a 95% confidence level. For the three types of samples studied the estimated standard deviation was less than 0.03 mg kg-1 (n = 3). The analytical frequency was 95 h-1, the limit of detection was 0.004 mg kg-1 and the limit of quantification was 0.013 mg kg-1. The recovery study shows results between 98.4% and 104.2%. The FBA method showed better analytical features when compared with previous automatic flow methods. Thus, the automated method proposed is potentially useful as an alternative for the determination of other ions in similar samples or in other viscous matrices without external pretreatment. / Neste estudo, um analisador em fluxo-batelada (FBA) foi desenvolvido e seu desempenho foi avaliado na determinação de Fe (III) em óleos comestíveis sem pré-tratamento da amostra. O método utiliza a reação entre os íons Fe(III) e o tiocianato solubilizado em meio orgânico. O complexo vermelho formado foi monitorado utilizando um diodo emissor de luz (LED, λmax = 520 nm) e um fototransistor acoplados ao interior da câmara de mistura por meio de fibras ópticas. As soluções-padrão foram preparadas em linha e todas as etapas de análise foram efetuadas através de simples alterações nos parâmetros operacionais no programa de gerenciamento do sistema. Ao comparar os resultados obtidos com o método proposto e com o de referência, não foram observadas diferenças estatisticamente significativas ao se aplicar o teste t pareado com nível de confiança de 95%. Para os três tipos de amostras em estudo o desvio-padrão relativo estimado foi menor que 0,03 mg kg-1 (n = 3). A frequência analítica foi de 95 h-1, o limite de detecção foi 0,004 mg kg-1 e o limite de quantificação foi de 0,013 mg kg-1. Estudos com amostras fortificadas mostraram resultados de recuperação entre 98,4% e 104,2% para ambas as matrizes. De modo geral, o método proposto apresentou melhor desempenho analítico quando comparado com analisadores em fluxo automático anteriores. Assim, o método automático proposto é potencialmente útil como uma alternativa para a determinação de outros íons em amostras semelhantes aos óleos investigados ou em outras matrizes viscosas sem necessidade de um pré-tratamento.

La friture profonde de type batch a été étudiée dans le projet FUI Fry’In (Réf. AAP17, 2014-2018) dans le but de proposer des innovations de rupture pour des friteuses batch domestiques et professionnelles. La thèse a appuyé le projet sur la maîtrise de deux effets négatifs de la friture : i) la thermo-oxydation de l’huile responsable des mauvaises odeurs et produits de dégradation ainsi que ii) la prise d’huile généralement favorisée au détriment de son égouttage. L’étude a été réalisée en combinant des mesures directes (spectroscopie et imagerie infrarouges en mode ATR, photo-ionisation, mesures DSC, imagerie rapide…) et modélisation multi-échelle (écoulement de l’huile et égouttage lors du retrait, description lagrangienne des réactions en présence d’un écoulement, couplage avec les ciné-tiques de dissolution de l’oxygène). La complexité du processus de thermo-oxydation a été réduite en considérant les hydroperoxydes comme une forme de stockage organique de l’oxygène, qui propage l’oxydation dans des régions en anoxie. Leur décomposition produit de nombreux composés de scission, dont la nature est influencée par les conditions locales de température et de concentration en oxygène. La prise d’huile a été décrite comme le bilan net entre l’huile charriée au moment du retrait et l’huile égouttée. L’égouttage a été étudié sur des barreaux métalliques et des produits réels. Il se conduit à la formation de quatre à huit gouttes en quelques secondes. Les cinétiques de drainage anisothermes ont été prédites par un modèle mécanistique. Le mécanisme spécifique de prise d’huile en cours de friture a été aussi analysé ; il se produit uniquement dans le cas des produits préfrits congelés. / Batch deep-frying has been investigated within the collaborative project FUI Fry’In (ref. AAP17, 2014-2018) with the aim of proposing breakthrough innovations for small and medium size appliances. The PhD thesis was part of the project and focused on two specific adverse effects of deep-frying on food products: oil thermo-oxidation responsible for break-down products and off-flavors, and oil pickup process usually favored relatively to oil dripping. The work was carried out by combing direct measurements (FTIR-ATR spectroscopy and imaging, photoionization, DSC measurements, fast imaging…) and multiscale modeling (oil flow and oil dripping during product re-moval, Lagrangian description of reactions in aniso-thermal flows, coupling with oxygen dissolution kinetics). The complex problem of thermo-oxidation was split into simpler mechanisms by noticing that hydroperoxides are a kind of long-lived form of or-ganic oxygen, which trigger propagation in deep re-gions under anoxia. Their decomposition lead to various scission products, which were shown to be in-fluenced by both local temperature and oxygen con-centration. Oil uptake was described as the net balance between the amount of dragged oil during product removal and oil dripping at the tips of the product. The dripping process studied on both metal-lic sticks and real products occurs in less than few seconds and leads to a formation of four to eight drop-lets. The detailed drainage kinetics in anisothermal conditions were captured and predicted with the pro-posed mechanistic models. The specific mechanism of oil uptake during the immersion stage was eluci-dated and was shown to occur only in parfried frozen products.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-10-02T19:59:47Z No. of bitstreams: 1 ThatyaraMonteiro.pdf: 3528798 bytes, checksum: 12d3da9115c45896b4f14c67dbe3d20e (MD5) / Made available in DSpace on 2017-10-02T19:59:47Z (GMT). No. of bitstreams: 1 ThatyaraMonteiro.pdf: 3528798 bytes, checksum: 12d3da9115c45896b4f14c67dbe3d20e (MD5) Previous issue date: 2017-09-01 / Two novel and pioneering photoelectrochemical sensors were developed for determination of tert-butyl hydroquinone (TBHQ) in biodiesel and edible oil samples. The former based on composite formed by TiO2 nanoparticles and lithium tetracyanethylene (LiTCNE), and the last based on the sensitization of CdSe/ZnS quantum dots with LiTCNE. In both cases, indium tin oxide (ITO) was used as the work electrode surface. The LiTCNE/TiO2/ITO sensor showed a TBHQ photocurrent about 28-fold higher than the TiO2 sensor. The same was observed for the CdSe/ZnS/LiTCNE/ITO sensor, which presented a photocurrent for TBHQ about 13-fold higher than that presented by the electrode modified with CdSe/ZnS. Both developed sensors showed lower resistance to charge transfer than their non-sensitized components. They also demonstrated high selectivity to TBHQ, with high photocurrent for this compound in comparison to photocurrent responses to other phenolic antioxidants. The experimental conditions optimized for both sensors were: 0.1 mol L-1 of phosphate buffer solution pH 7.0 and applied potential to the working electrode of 450 mV, for the LiTCNE/TiO2/ITO sensor, and 0.1 mol L-1 of phosphate buffer solution pH 6.0, and potential of 400 mV for the CdSe/ZnS/LiTCNE/ITO sensor. In these conditions, the sensors presented a linear range of TBHQ response between 0.4 and 500 μmol L-1 for LiTCNE/TiO2/ITO sensor and between 0.6 and 250 μmol L-1 for the CdSe/ZnS/LiTCNE/ITO sensor, with limits of detection of 0.10 and 0.21 μmol L-1, respectively. The LiTCNE/TiO2/ITO sensor was applied in biodiesel samples for determination of TBHQ using standard addition method, showing recovery values between 96.8 and 98.2%. The CdSe/ZnS/LiTCNE/ITO sensor was applied in edible oil samples to detect TBHQ using an external calibration method, with recovery values between 98.25 and 99.83%. The photoelectrochemical sensors were successfully used to determine the TBHQ antioxidant in real samples of biodiesel and vegetable oil. / Dois novos e pioneiros sensores fotoeletroquímicos foram desenvolvidos para determinação de tert-butil hidroquinona (TBHQ) em amostras de biodiesel e de óleo comestível. O primeiro baseado no compósito formado por nanopartículas de TiO2 e tetracianoetileneto de lítio (LiTCNE), e o segundo baseado na sensibilização de quantum dots CdSe/ZnS com o LiTCNE. Em ambos os casos utilizou-se como eletrodo de trabalho o óxido de índio e estanho (ITO) como superfície eletródica. O sensor à base de LiTCNE/TiO2/ITO apresentou uma fotocorrente para o TBHQ cerca de 28 vezes mais elevada que o sensor à base de TiO2. O mesmo foi observado para o sensor à base de CdSe/ZnS/LiTCNE/ITO, que apresentou fotocorrente para o TBHQ cerca de 13 vezes maior do que à apresentada pelo eletrodo modificado com CdSe/ZnS. Ambos os sensores desenvolvidos apresentaram baixa resistência à transferência de carga em comparação a seus componentes não sensibilizados. Também demonstraram grande seletividade ao TBHQ, com alta fotocorrente para esse composto em comparação às respostas de fotocorrente para outros antioxidantes fenólicos. As condições experimentais otimizadas para ambos os sensores desenvolvidos foram, respectivamente: 0,1 mol L-1 de solução tampão fosfato pH 7,0 e potencial aplicado ao eletrodo de trabalho de 450 mV, para o sensor LiTCNE/TiO2/ITO, e 0,1 mol L-1 de solução tampão fosfato pH 6,0, e potencial de 400 mV, para o sensor CdSe/ZnS/LiTCNE/ITO. Nessas condições, os sensores apresentaram faixa linear de resposta de TBHQ entre 0,4 a 500 µmol L-1 para sensor LiTCNE/TiO2/ITO e entre 0,6 a 250 µmol L-1 para o sensor CdSe/ZnS/LiTCNE/ITO, apresentando limites de detecção de 0,10 e 0,21 µmol L-1 , respectivamente. O sensor LiTCNE/TiO2/ITO foi aplicado em amostras de biodiesel para determinação de TBHQ usando método de adição de padrão, mostrando valores de recuperação entre 96,8 e 98,2%. Já o sensor CdSe/ZnS/LiTCNE/ITO foi aplicado em amostras de óleo comestível para detecção de TBHQ usando método de calibração externa, com valores de recuperação entre 98,25 e 99,83%. Os sensores fotoeletroquímicos foram empregados com sucesso para determinação de antioxidante TBHQ em amostras reais de biodiesel e óleo vegetal.