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Dans cette thèse nous avons étudié différents aspects de l'interaction entre un atome et une surface diélectrique. Nous avons notamment recherché expérimentalement des situations où l'interaction de van der Waals à longue portée varie avec la population thermique de photons du vide, telle qu'imposée par un équilibre avec l'environnement. Une variation avec la température est prévue lorsqu'il y a un couplage virtuel résonnant en champ proche entre l'émission thermique de la surface (dans l'IR) et une absorption atomique. Notre recherche a porté sur l'interaction entre Cs(8P) et une surface de CaF2 en utilisant la spectroscopie de réflexion sélective. Jusqu'à présent, les valeurs expérimentales du coefficient C3 de l'interaction de van der Waals sont en contradiction avec les prédictions théoriques. Nous avons pourtant raffiné les prédictions théoriques en introduisant dans les calculs la dépendance en température de la constante diélectrique, à partir de nouvelles mesures de la réflectance sur des surfaces de saphir, CaF2 et BaF2 effectués à différentes températures. Nous avons, en outre, observé, sur une expérience auxiliaire d'absorption saturée, des raies inédites autour de la transition 6S1/2→8P, que nous avons attribuées à des dimères spécifiquement formés par nos faisceaux lasers. Ces raies apparaissent pour des densités de vapeur inhabituellement faibles. A un régime de plus faible distance de l'interaction atome-surface, où le potentiel combine attraction van der Waals et répulsion au voisinage immédiat de la surface, nous avons analysé la possibilité d'observer des oscillations de Bloch, en considérant le cas d'un atome d'Helium adsorbé sur une surface de LiF et soumis à une force externe.

Cette thèse porte sur l'étude de sources lasers à base d'ions Yb3+ pour une émission autour de 1um. Le premier objectif de ce travail était d'étudier des cristaux massifs dopés Yb3+ fabriqués au CIRIL pour réaliser des sources lasers en régime continu et en régime à impulsions brèves. Pour cela, nous avons concentré notre attention sur la matrice de CaF2 dopée Yb3+ qui combine les propriétés des cristaux (bonne conductivité thermique) et des verres (larges bandes d'émission). Bien que largement étudié par le passé, le CaF2 dopé par de l'ytterbium trivalent n'avait pas encore fait l'objet d'une étude spectroscopique détaillée. L'examen du fonctionnement laser a donc été précédé d'une étude spectroscopique pour de faibles et de forts taux de dopage en ions Yb3+. Les sites dits isolés ainsi que les agrégats d'ions terres rares ont pu être caractérisés clairement. Une étude laser expérimentale et théorique a ensuite été menée qui a conduit à d'excellentes performances, en régime continu ou femtoseconde, plaçant le CaF2:Yb3+ comme un des plus sérieux candidats pour ce type de source. Le second objectif de cette thèse était l'étude d'une source laser en optique intégrée émettant à 980 nm, utile dans le domaine des télécommunications (pompage des amplificateurs dopés erbium). Deux voies d'exploration ont été examinées, l'une sur des guides de SiO2:Yb,Ti,Ge fabriqués par pulvérisation magnétron réactive et l'autre sur des guides de CaF2:Yb3+ élaborés par implantation ionique. De premiers résultats expérimentaux ont été obtenus, et un modèle laser théorique nous a permis de prédire l'émission laser à 980 nm dans ce type de structure.

Le protéasome 26S est une macromolécule impliquée dans la dégradation de la majorité des protéines cellulaires. Parmi ces protéines, il y a les différents régulateurs de processus cruciaux tels que les protéines responsables de la progression du cycle cellulaire, de l’apoptose, des réponses inflammatoires, de l’activation de NF-B, de la présentation antigénique et de la différenciation cellulaire. Par conséquent, les inhibiteurs du protéasome sont des agents thérapeutiques dans des pathologies tels que le cancer, l’inflammation et les maladies auto-immunes. En effet, les inhibiteurs du protéasome sont connus pour induire la mort sélective des cellules cancéreuses tout en les rendant plus sensibles aux autres traitements anticancéreux existants (chimiothérapie, radiothérapie…). L’objectif de notre laboratoire est de développer des inhibiteurs non covalents du protéasome de structures peptidomimétiques fluorés ou non fluorés, et de montrer l’intérêt du fluor en chimie médicinale. Mon projet de thèse s’inscrit dans ce cadre. Dans un premier temps nous avons mis en évidence la grande diversité et la quantité des inhibiteurs du protéasome montrant ainsi l’importance de cette macromolécule comme cible dans le traitement du cancer. D’ailleurs, deux de ces inhibiteurs sont utilisés dans le traitement du myélome multiple et du lymphome du manteau et, plusieurs composés sont en études cliniques pour différents cancers. Nous avons aussi mis en évidence le bénéfice apporté par l’incorporation de groupement fluoré sur une molécule bioactive en particulier dans les structures peptidomimétiques. En revanche, ce rappel bibliographique a aussi montré que les peptidomimétiques contraints et fluorés sont peu décrits dans la littérature et le seul exemple à notre connaissance est l’analogue contraint et fluoré de la substance P contenant le motif (Z)-fluoroalcène.La deuxième partie de ces travaux de thèse s’est focalisée sur la conception, la synthèse et l’évaluation biologique d’inhibiteurs originaux du protéasome. Nous avons mis au point une synthèse facile et efficace de pseudopeptides possédant les motifs α et β-hydrazino acides et le motif β-hydrazino acide trifluorométhyle (schéma 1). Ces molécules inhibent de manière efficace le site CT-L du protéasome du lapin avec une IC50 de l’ordre du submicromolaire. Nous avons ainsi démontré que l’activité biologique est maintenue en remplaçant un α-amino acide par un scaffold α ou β-hydrazino acide. La pharmacomodulation effectuée autour de ces motifs nous a permis d’établir des relations structure-activité. Nous avons aussi mis au point un modèle de docking assez fiable qui va nous permettre de prédire le potentiel inhibiteur de nos futures molécules.Enfin, nous avons déterminé l’IC50 de nos molécules en utilisant la technique du FABS en RMN du 19F. Schéma1: voies d’accès aux peptidomimétiques contenant les motifs α et β-hydrazino acide et le motif β-hydrazino acide trifluorométhyl.Ces travaux de thèses ont été complétés par une méthodologie de synthèse portant sur le développement de nouveaux synthons contraints fluorés dans le but de les incorporer dans nos inhibiteurs de protéasome. Les cyclopropanes trifluorométhyles ont été obtenus en utilisant la réaction tandem de Michael, addition nucléophile suivie de cyclisation avec une excellente diastéréosélectivité pour certaines réactions. Les cyclopropanes obtenus ont été fonctionnalisés en amino acides ce qui faciliterait leur incorporation dans nos pseudopeptides. Les N-aminoaziridines fluorés ont été synthétisés à partir d’oléfines fluorés et de précurseurs de nitrène en présence de diacétate d’iodobenzène (PhI(OAc)2. L’incorporation de ces nouveaux scaffolds dans la structure de nos inhibiteurs de protéasome est en cours de réalisation dans le laboratoire. / The proteasome is a multicatalytic protease complex that is responsible for the ubiquitin-dependent turnover of cellular proteins. Proteasome substrates include misfolded or misassembled proteins as well as short-lived components of signaling cascades that regulate cell proliferation and survival pathways. Inhibition of the proteasome leads to an accumulation of substrate proteins and results in cell death. The proteasome consists of a 20S proteolytic core and two 19S regulatory caps that assemble with the core at either end to form a 26S complex. Clinical validation of the proteasome as a therapeutic target in oncology has been provided by bortezomib, a dipeptide boronic acid, which is approved for the treatment of patients with multiple myeloma1and mantle cell lymphoma. In the first part of my PhD, I designed (by the help of molecular modeling) and synthesized an original series of proteasome inhibitors introducing fluorinated peptidomimetics. Fluorine atom is able to favour hydrogen bond and to increase hydrophobicity and metabolic stability of the molecules. I also synthesized a series of non fluorinated peptidomimetics containing hydrazino acid moieties as proteasome inhibitors. Thereby, we designed and synthesized a library of 50 molecules that allowed us to establish a structure-activity relationship. The biological evaluation showed that half of these compounds have a micromolar IC50 (inhibitor concentration giving 50% inhibition). Then we decided to test the inhibitor activity of our synthesized molecules by 19F NMR using the FABS technique. So we developed a fluorine substrate for screening and determination of IC50 of our potential protéasome inhibitors. In order to increase the activity of our molecules and according to encouraging observation by molecular modelling, we decided to introduce constrained scaffolds such as trifluoromethyl cyclopropane or trifluoromethyl N-aminoaziridine scaffolds in our peptidomimetics structures. So we needed trifluoromethyl cyclopropane and trifluoromethyl N-aminoaziridine amino acids that could be easily incorporate in peptidic structure. To our knowledge there is no precedent on the synthesis of fluorinated N-aminoaziridines or trifluoromethyl cyclopropane β-amino acids which allowed us to develop a new synthesis methodology of these scaffolds. First, I synthesized different trifluoromethyl N-Aminoaziridine with several protective groups. The reaction of N-Aminoaziridine was performed in DCM with K2CO3 as base and (Diacetoxyiodo)benzene. For the synthesis of trifluomethyl cyclopropane β-amino acid, we used the cyclopropanation of Michael acceptors (tandem Michael Additions-Nucleophilic Cyclization (MA-NC)). Encouraged by this result and in order to develop different scaffolds trifluoromethyl cyclopropanes, we screened other nucleophiles. These scaffolds have been functionalized to amino acid in order to introduce it in peptidic structure.

A cárie dentária é um dos maiores problemas de saúde pública dentro das patologias bucais ao nível mundial. Este estudo objetivou avaliar a prevalência de cárie e de fluorose dentária em adolescentes das regiões urbana e suburbana do município de Maputo e identificar a sua associação com placa bacteriana, estado nutricional, frequência do consumo de açúcar e concentração de flúor na água de abastecimento. A amostragem das escolas foi feita por conglomerados, composta por cinco escolas públicas urbanas e cinco suburbanas, tendo com unidades amostrais 601 adolescentes com 12 anos de idade, selecionados aleatoriamente. Os exames foram realizados por um examinador calibrado, sob condições padronizadas, usando índice CPOD, índice de fluorose, PHP e IMC. Foi aplicado um questionário para registrar o consumo de açúcar e foi realizada a análise da água de abastecimento. A análise bivariada foi utilizada para verificar diferenças de CPOD, fluorose, placa bacteriana, estado nutricional, frequência do consumo do açúcar e concentração de flúor na água de abastecimento público entre as regiões urbanas e suburbanas. A Correlação de Pearson foi aplicada para verificar associação entre CPOD e PHP. O nível de significância adotado foi de 5%. O CPOD encontrado foi 0,99 (± 1,65). As crianças em escolas urbanas apresentaram menor prevalência de cárie dentária (CPOD = 0,84 ± 1,49) em relação às crianças em escolas suburbanas (CPOD = 1,14 ± 1.80) (p = 0,03). Apenas 8,15% apresentaram graus de fluorose entre muito leve a moderada. A maioria das crianças apresentaram higiene bucal deficiente. Os casos de desnutrição foram mais encontrados nas escolas suburbanas (n = 109; 36,22%) do que nas escolas urbanas (n = 66; 22,00%), (p <0,00). A frequência de consumo do açúcar foi maior entre os escolares urbanos em comparação com suburbanos (p <0,00). O nível de flúor na água de consumo nas escolas urbanas foi de 0,4 ppm F, superior ao nível de flúor nas escolas suburbanas, que foi de 0,2 ppm F. Os resultados demosntraram que a cárie dentária não deve ser considerada um grande problema de saúde pública em Maputo. As áreas urbanas e suburbanas apresentaram distribuição desigual na prevalência de cárie, estado nutricional e nível de flúor na água de abastecimento, evidenciando a necessidade de intervenção no grupo de maior de risco. / Dental caries is the one of the largest public health problem in oral health worldwide. This study aimed to evaluate the prevalence of dental caries and dental fluorosis in children from urban and suburban area of the Maputos city and identify its association with dental plaque, nutritional status, frequency of consumption of sugar and the concentration of fluoride in the water supply. Sampling of schools was made by conglomerates, composed by five urban public schools and five suburban, with 601 adolescents 12 years of age, selected randomly. Clinical examinations were performed under standardized conditions by a calibrated examiner using DMFT index, index of fluorosis, PHP, BMI. It was applied a questionnaire about consumption of sugar and was made analysis of water supply. Bivariate analysis was used to verify differences in DMFT, fluorosis, dental plaque, nutritional status, frequency of consumption of sugar and concentration of fluoride in the public water supply between the urban and suburban areas. The Pearson\'s correlation was applied to verify correlation between DMFT and PHP. The level of significance was set at 5%. The mean DMFT was 0.99 (± 1.65). Children in urban schools had lower prevalence of dental caries (DMFT = 0.84 ± 1.49) in comparison with children in suburban schools with high prevalence (DMFT = 1.14 ± 1.80) (p = 0.03). Only 8.15% had very mild to moderate fluorosis score. Most of children presented poor oral hygiene. Cases of malnutrition were found in most suburban schools (n = 109; 36.22%) than in urban schools (n = 66; 22.00%) (p=0.03). The frequency of sugar consumption was higher among urban children compared to suburban schools (p <0.00). The level of fluoride in water consumption in urban schools was 0.4 ppm F, above the level of fluoride in suburban schools, which was 0.2 ppm F. The results showed that dental caries should not be considered a public health problem in Maputo. The urban and suburban areas presented inequity distribution in the prevalence of dental caries, nutritional status and level of fluoride in water supply, highlighting the need for intervention in the highest risk.

O objetivo deste estudo foi comparar, in vitro, empregando diferentes métodos de análise, a ação de superfície de alguns enxaguatórios bucais experimentais para a prevenção/controle da erosão dental causada por ácido clorídrico incorporando-se diferentes princípios ativos. Um enxaguatório bucal experimental sem aditivos, um enxaguatório para erosão disponível comercialmente, Elmex Erosion® (AmF/NaF/SnCl2) (ELM), e um enxaguatórios acrescidos de 4 diferentes aditivos foram testados quanto a sua capacidade de proteção contra erosão em um modelo de erosão-remineralização, onde as variáveis resposta foram a alteração da micro e da nanodureza e as quantidades de cálcio e fosfato liberadas em solução, determinadas por espectrometria de emissão óptica. Os aditivos utilizados foram: Caseína (CAS 5 g/L), Hexametafosfato de sódio (HMP 0,2 g/L), Tetrafluoreto de titânio (TiF4 3,4g/L) e Fluoreto estanhoso (SnF2 8,7g/L). Espécimes de esmalte bovino foram incluídos em resina acrílica e polidos. Esses foram distribuídos nos grupos (n=8) e ciclados da seguinte forma: (1) Imersão em 20 ml de ácido clorídrico (HCl) a 0,01M pH = 2,4 por 10 s, (2) imersão em 20 ml de saliva artificial por 60 s, (3) imersão em 20 ml de solução teste por 30 s e (4) imersão em 20 ml de saliva artificial por 60 s. Este ciclo foi repetido por 3 vezes por um dia e as soluções utilizadas foram armazenadas para posterior avaliação. Para microdureza, os espécimes tratados com ELM e SnF2 apresentaram os maiores valores de dureza, os quais foram significantemente diferentes de TiF4, que apresentou o menor valor. O ELM, SnF2, CAS e HMP foram semelhantes estatisticamente ao C. Para nanodureza, o TiF4 apresentou menor valor médio de dureza e significantemente diferente do C. O SnF2, ELM, CAS e HMP apresentaram-se estatisticamente semelhantes ao C. Na análise de perda de cálcio da ciclagem final, ELM e HMP resultaram em menor perda de cálcio e estatisticamente diferentes do C. Na primeira imersão, todos os grupos testados, exceto a caseína, mostraram significantemente menor perda que o C e, na segunda, não foi constatada diferença estatística significante. Na análise de perda de fosfato da ciclagem final, ELM e TiF4 apresentaram as menores perdas de íons, sendo significantemente diferente do C. Na primeira e segunda imersões, somente ELM mostrou-se estatisticamente diferente do C. Conclui-se que o ELM, o HMP e o TiF4 protegeram a superfície de esmalte quanto a perda de íons porém os testes de dureza não detectaram essa proteção. / The objective of this study was to compare, in vitro, using different methods of analysis, the effect on surface of an experimental mouthrinse modified with different active ingredients for the prevention / control of dental erosion caused by hydrochloric acid. An experimental mouthrinse without additives, a commercially available mouthwash for erosion Elmex Erosion ® (AmF/NaF/SnCl2) (ELM) and four mouthrinses added 4 different additives were tested for their ability to protect against erosion in a model of erosion-remineralization, where the response variables were the change of micro-and nanohardness and the quantities of released calcium and phosphate in solution, determined by optic emission spectrometry. The additives used were: casein (CAS 5 g/L), sodium hexametaphosphate (HMP 0.2 g/L), titanium tetrafluoride (TiF4 3.4 g/L) and stannous fluoride (SnF2 8.7 g/L). Bovine enamel specimens were embedded in acrylic resin and polished. They were ramdomily distributed in groups (n=8) and submitted to the following cycle: (1) immersion in 20 ml of 0,01M hydrochloric acid (HCl), pH = 2.4 10 s, (2) immersion in 20 ml of saliva artificial for 60 s, (3) immersion in 20 ml of test solution for 30 seconds and (4) immersion in 20 ml of artificial saliva for 60 s. This cycle was repeated three times during the same day and the solutions were stored for later evaluation. For microhardness, the specimens treated with ELM and SnF2 showed the highest values of hardness, being significant different from TiF4 solution, which presented the lowest value. The ELM, SnF2, CAS and HMP were statistically similar to C. For nanohardness, the TiF4 had the lowest value of hardness, being significant different from C. The SnF2, ELM, CAS and HMP were statistically similar to C. In the calcium analysis after the last cycle, ELM and HMP resulted in less calcium loss, which was significantly different from C. After the first immersion, all groups tested, except casein, showed statistically lower calcium loss when compared to group C and there was no difference in statistical analysis of loss of phosphate in the second. In analysis of phosphate loss after the final cycle, ELM TiF4 showed the lowest losses being significant different from C. After the first and the second cycles, only ELM was statistically different from C. It can be concluded that the ELM, HMP and TiF4 protect the enamel surface against ions loss but the hardness tests could not detect this protection.

Fluorhaltige-Koordinationspolymere (FCPs) wurden durch mechanochemische Reaktionen synthetisiert. Die Erdalkalimetallhydroxide, die in ihrem Wassergehalt variieren, wurden als anorganische Quellen verwendet. Die perfluorierten Benzol Dicarboxylsäuren und ihre fluorfreien Analoga wurden als organische Linker verwendet. Die erhaltenen FCPs werden mit den fluorfreien Verbindungen (CPs) verglichen, die unter den gleichen Mahlbedingungen synthetisiert wurden. Der Austausch von Wasserstoff- durch Fluoratome beeinflusst sowohl die thermischen als auch die strukturellen Eigenschaften der FCPs. Letztere werden auch von den Unterschieden der Geometrien und von der Natur der organischen Linker beeinflusst. Während des Mahlprozesses dient Wasser dabei hauptsächlich als Vermittlermedium und zur Stabilisierung der neuen Strukturen. Die Unterschiede in den Kationengrößen zwischen Ca2+- und Sr2+-Ionen wirken sich geringfügig auf ihre Koordination durch die Dicarboxylatanionen aus. Hier kristallisieren Ca- und Sr-Verbindungen zumeist isomorph. Im Gegensatz dazu beeinflusst der große Ionenradius der Ba2+-Kationen die lokalen Koordinationsumgebungen. Die durch Mahlen erhaltenen Verbindungen sind hydratisiert und weisen eine kleine spezifische Oberfläche auf, die nach der thermischen Behandlung zunehmen kann. Die FCPs sind bis zu 300 °C stabil, während die CPs sich erst oberhalb von 400 °C zersetzen. Die hydratisierten Proben wandeln sich beim Tempern in neue dehydratisierte Phasen um. Die Phasenumwandlung kann reversible ablaufen. Zusätzlich wurde der Effekt des Austausches einer Carboxylgruppe durch eine Aminogruppe in einem organischen Liganden untersucht. In den CPs auf der Basis von Anthranilsäure beeinflussen die unterschiedlichen Kationengrößen der Ca2+-, Sr2+-, und Ba2+-Ionen sowohl die Koordinationsumgebung als auch die Dimensionalität der CPs.Die physikalisch-chemischen Eigenschaften der neuen Materialien wurden systematisch durch verschiedene analytische Techniken. / A series of fluorinated coordination polymers (FCPs) were mechanochemically synthesized using alkaline earth metal hydroxides (M = Ca, Sr, Ba) that vary in their water content as inorganic sources. The perfluorinated benzene-dicarboxylic acids and their fluorine-free analogs were used as organic linkers. The obtained FCPs are compared to their synthesized fluorine-free counterparts (CPs) under the same conditions. The presence of fluorine influences both thermal and structural properties of the resulting FCPs. The latter are also strongly affected by the difference in geometries and nature of organic linkers. Water introduced to grinding acts as a mediator for the milling process and as a reactant for stabilizing the resulting structures. The difference in cation size between Ca2+- and Sr2+-ions has a minor effect on their coordination with perfluorinated or fluorine free benzene-dicarboxylate anions. Here, Ca- and Sr-compounds crystallize isomorphously (an exception was recorded for ortho-phthalate systems). In contrast, the relatively larger size of Ba2+-cation strongly influences the coordination environment. The obtained compounds by milling are hydrated and exhibit small surface areas that can increase after thermal post-treatment. The FCPs are stable up to 300 ˚C. On the other hand, the nonfluorinated CPs begin to decompose above 400 ˚C. The hydrated samples transform into new dehydrated phases upon thermal annealing. The hydrated-dehydrated phase transformation can be reversible. Moreover, the effect of replacement of one carboxylic group by an amino group in an organic ligand was explored. In the CPs based on anthranilic acid, the variations in cation size between Ca2+-, Sr2+-, and Ba2+-ions affect both coordination environment and dimensionality of the resulting CPs. The physicochemical properties of the new materials were systematically investigated applying different analytical techniques.

A 18FCH é um biomarcador promissor para imagem de tumores usando a tecnologia PET, sendo eficaz no diagnóstico de tumores metastáticos e específico para tumores cerebrais, de próstata, de pulmão, entre outros. Apesar de já ser utilizada em alguns países como na França, Alemanha, Eslovênia, Polônia, România e Portugal, a 18FCH ainda não é produzida nem comercializada no Brasil. Este trabalho propôs o desenvolvimento de um novo radiofármaco baseado em colina marcada com o isótopo 18F para diagnóstico de imagens PET por ser uma demanda crescente na medicina nuclear nacional. Também foi proposto o desenvolvimento de ensaios para o controle de qualidade de modo a avaliar o radiofármaco antes de sua utilização em pacientes; testes in vitro de toxicidade em células não tumorais (MRC-5), avaliando possíveis alterações na proliferação celular causadas pelas impurezas do radiofármaco; e, testes de saturação da interação da 18FCH com células tumorais (PC-3 e U-87) e a competição com HC-3 e DMAE, realizados para caracterizar a eficiência da captação do radiofármaco por células tumorais que expressam o transportador de colina CHT. A 18FCH foi sintetizada por duas etapas principais, a primeira pela reação do dibromometano com fluoreto-18, assistida por Kryptofix2.2.2, formando o 18F-fluorobromometano (18FBrCH2) e, em seguida, o 18FBrCH2 reagiu com o segundo precursor, DMAE, gerando o produto final,18FCH. O tempo de síntese foi de 45 minutos. A 18FCH foi obtida com rendimento radioquímico de 4,68 a 8,32%, pureza radioquímica maior que 99% e mostrou-se estável por até 8 horas após a sua produção. As metodologias analíticas testadas foram adequadas para o uso rotineiro no controle de qualidade da 18FCH. A avaliação do potencial citotóxico das impurezas da 18FCH, pelo teste clonogênico, mostrou que, nas concentrações avaliadas, os componentes não alteram a capacidade proliferativa das células sadias humanas. A interação da 18FCH com as linhagens celulares foi saturável, com ligação específica maior que 94%, atestando a eficácia do radiofármaco. O HC-3 e DMAE mostraram significativa inibição da captação do radiofármaco, demonstrando que, sua captação nestas células ocorre parcialmente, pelo transportador CHT. Os valores de IC50 para HC-3 foram de 795,9+ 221,1; 409,3 + 353,6 e 778,4 + 95,3M para PC-3, U-87 e MRC-5, respectivamente e para DMAE foram de 11,0 + 8,7; 4,7 + 1,2 e 6,3 + 2,2M para PC-3, U-87 e MRC-5, respectivamente, mostrando-se potentes inibidores da captação da colina. Todos os testes realizados contribuíram, em parte, para o processo de registro conforme normas da ANVISA.

Les mousses extinctrices sont utilisées sur les feux de catégorie B (solvants inflammables). L’efficacité des mousses actuelles contenant des agents moussants fluorés est apportée par la formation d’un film aqueux à la surface du carburant enflammé. Les entreprises recherchent et développent de nouveaux agents moussants sans fluor car ce type de tensioactif est nocif pour l’environnement et la santé. Des mousses très stables sont nécessaires pour qu'une couche épaisse de mousse résiste aux températures élevées et au démoussage par le solvant et évite ainsi la ré-inflammation.Dans ce travail, l’amélioration de la stabilité de la mousse a été réalisée en utilisant des épaississants dans une solution moussante avec des tensioactifs non fluorés. Des polysaccharides tels que la gomme xanthane ont été utilisés et ses interactions avec des tensioactifs ont été étudiés. Les complexes formés par ces interactions ont été utilisés dans le but d’améliorer la stabilité de la mousse et sa résistance aux flammes. Ceci engendre des mousses de plus faible moussabilité mais de plus grande stabilité. Des tests à échelle réduite ont été réalisés selon la norme EN1568 et ont montré l’efficacité de l’addition de gomme xanthane. Ces formulations innovantes associant des polysaccharides et des agents moussants sont de bonnes alternatives aux formules contenant des tensioactifs fluorés. Le mécanisme d’action des hydrotropes améliorant la moussabilité a aussi été étudié / Firefighting foams are used on class B fires (flammable solvents). The efficiency of currently used foams containing fluorinated foaming agents is ensured by the formation of an aqueous thin film on top of the burning solvent. The formation of such film requires the use of fluorinated surfactants that specifically adsorb at the water-air interface. Companies currently develop fluorine-free products for firefighting foams because this kind of surfactants is harmful for the environment and health. Very stable foams are necessary to the formation of a thick layer of foam that resists high temperatures and defoaming by the solvent, preventing fire re-ignition.In this work, improved foam stability was achieved by using thickeners in the foaming fluid together with the non-fluorinated surfactants. Polysaccharides such as xanthan gum were used and their interactions with surfactants were investigated. Complex species formed by such interactions were used in order to improve foam stability and resistance against flames. This causes a lower foamability but higher stability of foams. Small scale fires extinguishing experiments performed following the standard EN1568 showed the efficiency of xanthan gum addition. These innovative formulations combining polysaccharides and foaming agents are suitable alternatives to those containing fluorinated surfactants. The action mechanism of hydrotropes improving foamability has also been studied

Poly- and perfluoroalkyl substances (PFAS) are ubiquitous contaminants across the globe, can bioaccumulate in aquatic taxa, and potentially biomagnify in food webs. Consequently, research examining the influence of PFAS on wildlife is warranted. Amphibians are sensitive to contaminants such as PFAS because of their porous skin and associations with aquatic habitats where contaminants accumulate. Because PFAS tend to bioaccumulate and can adversely affect the endocrine system, there is a need to examine uptake rates to inform ecotoxicology studies, as well as a need to examine sublethal effects. To address these knowledge gaps I conducted two experiments. First, I exposed larval northern leopard frogs (<i>Rana pipiens</i>), American toads (<i>Anaxyrus americanus</i>), and eastern tiger salamanders (<i>Ambystoma tigrinum</i>) to PFAS chemicals perfluorooctanoic acid (PFOA) or perfluorooctane sulfonate (PFOS) at concentrations of 10 or 1000 ppb for 10 days and sampled them every 48 hours during the exposure period. In the next experiment, I examined the effects of PFAS exposure via contaminated substrate on the survival and growth of post metamorphic amphibians of the same species. I found that, for all species, body burdens often reached steady state within 48 to 96 h of exposure. Steady-state body burdens of PFOA ranged from 3,819–16,481 ng/g dry weight among treatments and species (corresponding BCFs of 0.5 to 2.5), while PFOS body burdens ranged from 6,955–489,958 ng/g dry weight (corresponding BCFs of 47–259) among treatments and species. These data suggest that steady state is rapidly reached in larval amphibians exposed to PFAS, particularly regarding PFOS. This reflects a high potential for trophic transfer of PFAS within food webs because amphibians are often low in trophic position and are important prey for many aquatic and terrestrial species. In post-metamorphic amphibians, there was no influence of PFAS on survival or mass. However, significant effects on snout-vent length were observed in all species, and body condition differences were observed for two of my species. I found that all leopard frogs increased in scaled mass index (SMI) when exposed to a PFAS treatment, indicating an increased body condition. Toads exhibited a more variable SMI pattern across treatments, with no outstanding trends, and tiger salamanders did not differ significantly across treatments. These data suggest that sublethal effects vary greatly depending on the species, possibly due to life history traits. Future research examining biomagnification potential is warranted to determine the influence of PFAS on food webs. Additionally, there is a need to determine the physiological mechanisms underlying the observed effects of PFAS exposure.<br>