O consumo de cocaína e crack no Brasil é um problema de saúde pública, ainda mais grave quando realizado por gestantes, que colocam em risco a sua vida e a do feto. A identificação dessas substâncias através de cromatografia gasosa acoplada à espectrometria de massas e utilizando como matriz biológica o mecônio, é uma técnica eficiente para detecção da exposição fetal à cocaína. O mecônio apresenta algumas vantagens em relação às outras matrizes biológicas como uma ampla janela de detecção dos analitos e de fácil coleta por ser não-invasiva. Diante disso, o objetivo do presente estudo foi desenvolver e validar uma metodologia de preparo do mecônio para identificação de cocaína, benzoilecgonina, cocaetileno e o éster metilanidroecgonina em seus extratos, usando a cromatografia gasosa acoplada a espectrometria de massas (CG-EM). Os analitos foram inicialmente extraídos com metanol, sendo posteriormente, purificados usando cartuchos de extração em fase sólida do tipo Bond Elut Certify I. A determinação desses analitos foi realizada usando um CG-EM do tipo íon trap, no modo full scan de detecção. O método foi validado, segundo critérios estabelecidos pela ANVISA, na faixa de linearidade de 20 a 1000 ng/g para a cocaína e o cocaetileno; 40 a 1500 ng/g para a benzoilecgonina e 60 a 1500 ng/g para o éster metilanidroecgonina, usando 0,5 g de mecônio por análise. A resposta do detector apresentou-se linear na faixa estudada e o limite de detecção encontrado foi de 10ng/g para a cocaína; 20ng/g para o cocaetileno; 30ng/g para a benzoilecgonina e 40 ng/g para o éster metilanidroecgonina. O coeficiente de variação intra-ensaio variou de 3,01% a 10,15% e o inter-ensaio variou entre 5,31% a 11,12%; a exatidão variou entre 91,47% e 105,31%. A recuperação encontrada foi superior a 56,30%. A especificidade foi determinada para os seguintes interferentes: AAS (ácido acetilsalicílico), alprazolam, anfetamina, cafeína, dipirona, efedrina, fenilefrina, fluoxetina, metoclopramida, nicotina, sulfato ferroso e THC (tetraidrocanabinol). Após o término da validação, o método foi aplicado em amostras de mecônio coletadas de recém-nascidos no Hospital das Clínicas da Faculdade de Medicina de Ribeirão Preto (HCFMRP USP). A coleta destas amostras foi realizada após a autorização das mães em participarem da pesquisa, através da assinatura do Termo de Consentimento Livre e Esclarecido, e após preencherem um questionário sobre consumo de drogas. O método desenvolvido e validado mostrou ser eficiente na identificação de cocaína, metabólitos e derivados em mecônio. / Cocaine and crack use is an important public health problem in Brazil, even though when this is made by pregnants, risking the babies lives besides their own. The identification of such substances through gas chromatograph-mass spectrometry using meconium as biological matrix is highly efficient on detecting fetal exposure to cocaine. The meconium presents some advantages in comparison with other matrices such as analite wide window detection and collection facilities by non-invasive methods. The purpose of this study was to develop and validate a method for meconium sample preparation for a gas chromatography-mass spectrometry (GC-MS) confirmation of meconium extracts for cocaine, benzoylecgonine, cocaethylene and anhydroecgonine methyl ester. The analytes were initially extracted from the matrix by methanol. Then, a solid-phase extraction with Bond Elut Certify I cartridges was applied. Analytes were determined in a GC-MS ion trap, full scan mode. The method was validated in the range of 20 -1000 ng/g for cocaine and cocaethylene; 40 -1500 ng/g for benzoylecgonine and 60 -1500 ng/g for anhydroecgonine methyl ester, using 0.5 g of meconium per assay. The detector response was linear in the studied range and limit of detection were found to be 10ng/g to cocaine; 20ng/g to cocaethylene; 30ng/g to benzoylecgonine and 40 ng/g to anhydroecgonine methyl ester. Intra-batch coefficients of variation oscillated between 3.01% and 10.15% and inter-batch oscillated between 5.31% and 11.12%; accuracy were in range 91.47% - 105.31%. The recoveries were higher than 56.30%. Selectiviy was determined for these interferents: AAS (acetylsalicylic acid), alprazolam, amphetamine, caffeine, dipyrone, ephedrine, phenylephrine, fluoxetine, metoclopramide, nicotine, iron sulfate and THC (tetrahydrocanabynol). Finally, the method was applied to analysis of meconium collected from newborns in the Hospital das Clínicas da Faculdade de Medicina de Ribeirão Preto (HCFMRP USP). The sample collections were made after mothers´s authorization, and after they signed a term and answered a self-report about use of drugs. The developed and validated method was efficient on identification of cocaine, metabolites and derivatives in meconium.

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-06-20T12:18:52Z No. of bitstreams: 1 2016 - Juarez Vicente.pdf: 4177115 bytes, checksum: 7c081fec8011e87e4bca3d5c9ea310ed (MD5) / Made available in DSpace on 2017-06-20T12:18:52Z (GMT). No. of bitstreams: 1 2016 - Juarez Vicente.pdf: 4177115 bytes, checksum: 7c081fec8011e87e4bca3d5c9ea310ed (MD5) Previous issue date: 2016-01-28 / The omega-3 (?-3) is a class of essential fatty acids, of major importance for the metabolism of various functions of the body, highlight for the prevention of cardiovascular diseases, immunological and anti - inflammatory, colon cancer, promotes developing brain and retina. The fatty acids of the series ?-3 and ?-6 are precursors of polyunsaturated long chain fatty acids as arachidonic (AA), eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), the latter considered the most important for developing neonatal and together with the AA are the main components of brain fatty acids (Silva et al., 2007). Microencapsulation employing the formation of simple emulsions is a strategy that aims to maintain the stability of omega-3 and permanence of their functional activities upon exposure to the same harsh conditions as oxidative processes. Biopolymers such as proteins and carbohydrates (natural) are components that assist in maintaining the physical and morphological stability of these emulsions employed for microencapsulation. Likewise, to give the product improvements in the rheological, nutritional and functional properties. Thus, this thesis aims to study the formation of micro-emulsions physically and morphologically stable and their behavior rheological properties of heat and oxidative stability of omega-3 in polymeric systems formed with ovalbumin (natural surfactant) and their interactions with natural polysaccharides (pectin and xanthan gum), compared to a standard system with synthetic surfactant (Tween 80) in the microencapsulation of omega-3 of Sacha Inchi (Plukenetia volubilis L.) oil. With this work we aim to also study the behavior of oxidative Sacha Inchi oil and its inclusion as a component in other foods in microencapsulated form. / O ?mega-3 (?-3) ? uma classe de ?cidos graxos essenciais, de reconhecida import?ncia para o metabolismo de diversas funcionalidades do organismo, destacam-se a preven??o de doen?as cardiovasculares, imunol?gicas e anti-inflamat?rias, c?ncer de c?lon, favorece o desenvolvimento cerebral e da retina. Os ?cidos graxos das s?ries ?-3 e ?-6 s?o precursores dos ?cidos graxos poli-insaturados de cadeia longa, como araquid?nico (AA), eicosapentaenoico (EPA) e docosahexaen?ico (DHA), este ?ltimo considerado o mais importante para o desenvolvimento neonatal e junto com o AA s?o os principais componentes dos ?cidos graxos cerebrais. A microencapsula??o empregando a forma??o de emuls?es simples ? uma estrat?gia que objetiva manter a estabilidade do ?mega-3 e a perman?ncia de suas atividades funcionais frente ? exposi??o do mesmo a condi??es adversas como processos oxidativos. Os biopol?meros como prote?nas e carboidratos (naturais) s?o componentes que auxiliam na manuten??o da estabilidade f?sica e morfol?gica destas emuls?es empregadas para microencapsula??o. Da mesma forma, conferem ao produto melhorias nas propriedades reol?gicas, nutricionais e funcionais. Com isso, objetiva-se nesta tese estudar a forma??o de micro-emuls?es f?sica e morfologicamente est?veis e seus comportamentos reol?gicos, propriedades calorim?tricas e estabilidade oxidativa do ?mega-3 nos sistemas polim?ricos formados com Ovalbumina (surfactante natural) e suas intera??es com polissacar?deos naturais (Pectina e Goma Xantana), comparado a um sistema padr?o com surfactante sint?tico (Tween 80) na microencapsula??o do ?mega-3 do ?leo de Sacha Inchi (Plukenetia volubilis L.). Com esse trabalho objetiva-se tamb?m o estudo do comportamento oxidativo do ?leo de Sacha Inchi e sua inser??o como componente em outros alimentos na forma microencapsulada.

Orientador: Marcelo Alexandre Prado / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-21T09:52:53Z (GMT). No. of bitstreams: 1 MirandaeSilva_LigiaMaria_M.pdf: 148256 bytes, checksum: 789cac2002bb2e8dcb1bf70832d395b6 (MD5) Previous issue date: 2012 / Resumo: O crescente aumento populacional em escala mundial, tornou necessário um grande esforço por parte da agricultura para aumentar, a cada ano, a produção de alimentos para atender as necessidades do mercado externo e interno do Brasil. Recursos técnicos e científicos passaram então, a serem aplicados em busca da melhoria na produção dos cultivos,principalmente mediante o uso de fertilizantes e praguicidas. Com isso, a sociedade se deparou com problemas de ordem de equilíbrio ambiental e saúde pública, pois devido à contínua diversificação dos fitoparasitas, surgem, a todo momento, reduções do período de tempo entre aplicações consecutivas, e mais importante talvez, usos de doses mais altas e emprego simultâneo de diferentes pesticidas, por parte dos agricultores, objetivando complementar ações específicas ou alcançar efeitos sinérgicos para maiores rendimentos na produção. Tal situação traz como conseqüência óbvia e direta, o aumento, inaceitável, dos riscos de contaminação do meio ambiente com resíduos químicos de defensívos da área agropecuarista prejudiciais à saúde, o que leva a inúmeros problemas relativos à segurança alimentar dos produtos consumidos, e à uma preocupação de âmbito nacional evidenciada pela criação do Programa de Análise de Resíduos de Agrotóxicos em alimentos (PARA) da ANVISA. O aumento na necessidade de detecção e quantificação destes compostos, acarretou o desenvolvimento de pesquisas no setor, a fim de atingir uma melhoria na eficiência,qualidade e rapidez de resposta nas análises. A possibilidade do estudo de não apenas um de cada vez, mas de até 300 compostos sendo extraídos, detectados e quantificados simultâneamente se tornou a saída mais viável, tanto qualitativa quanto economicamente, facilitando o monitoramento contínuo do fornecimento de produtos do setor alimentício pelos chamados métodos multiresíduos. O presentre trabalho teve como princípio a validação de um método multiresíduo para análise de 14 analitos usando uma técnica de alto poder de concentração e limpeza do extrato como o GPC (Gel Permeation Chromatography) e detecção e quantificação por GC-MS/MS e LC-MS/MS. Os pesticidas investigados englobam classes como: acaricidas, inseticidas, fungicidas, nematicidas e formicidas de aplicação foliar, em sementes ou em solo, sendo que o acefato, metamidofós, acetamiprido e o thiamethoxan foram extraídos de amostras de batata e feijão e analisados por LC-MS/MS e a azoxistrobina, bifentrina, carbofuran, chlorotalonil, clorpirifós, clorfenapir, etofenprox, famoxadone,metalaxil, procimidone e o tebuconazole em amostras de batata e tomate e analisados por GCMS/MS. Os limites de detecção (LD) encontrados variaram de 0,06 a 2,89µg/L, e os coeficientes de variação (CV), de 0,036 a 2,036%. As recuperações foram determinadas em cada tipo de amostras, e os valores encontrados estavam entre 93,34% e 109,67%. Nenhuma das matrizes utilizadas apresentaram resultados insatisfatórios e o método utilizado mostrouse robusto e de fácil aplicação para todos os analitos testados / Abstract: The growing population worldwide, has required a great effort on the part of agriculture to increase each year, the production of food to meet the needs of external and internal market of Brazil. Technical and scientific resources spent then, to be applied in pursuit of improved crop production, mainly through the use of fertilizers and pesticides.With this, the company encountered problems in the balance of environmental and public health, since due to the continuous diversification of plant parasites, arise at any moment,reductions in the time period between consecutive applications, and perhaps most important,uses more doses high and simultaneous use of different pesticides by farmers, aiming to complete specific actions or to achieve synergistic effects in producing higher yields. This situation brings obvious and direct consequence, the increase unacceptable risk of environmental contamination with chemical residues from pesticides in farms are harmful to health, which leads to numerous problems relating to food safety of the products consumed, and to a concern nationwide evidenced by the creation of the Program Analysis of Pesticide Residues in Food (TO) of ANVISA. The increase in the necessity for detection and quantification of these compounds, led the development of research in the sector in order to achieve an improvement in efficiency, quality and responsiveness in the analyzes. The possibility of studying not just one at a time, but up to 300 compounds being extracted,detected and quantified simultaneously output became more viable, both qualitatively and economically, facilitating continuous monitoring of the supply of products by the food industry called methods multiresidue. The principle presentre work was the validation of a multiresidue method for analysis of 14 analytes using a technique of high power concentration and cleanup of the extract as GPC (Gel Permeation Chromatography) and detection and quantification by GC-MS/MS and LC- MS / MS. The pesticides investigated include classes such as acaricides, insecticides, fungicides, insecticides and nematicides foliar, seed or soil,and acephate, methamidophos, and Acetamiprid thiamethoxan were extracted from samples of potatoes and beans and analyzed by LC-MS / MS and azoxystrobin, bifenthrin, carbofuran,chlorothalonil, chlorpyrifos, chlorfenapyr, etofenprox, famoxadone, metalaxyl, procymidone and tebuconazole in samples of potato and tomato and analyzed by GC-MS/MS. The limits of detection (LOD) ranged from 0.06 to 2.89 mg / L, and the coefficients of variation (CV), 0.036 to 2.036%. The recoveries were determined for each type of samples, and the values were between 93.34% and 109.67%. None of the arrays used had unsatisfactory results and method proved to be robust and easy to apply for all analytes tested / Mestrado / Ciência de Alimentos / Mestra em Ciência de Alimentos

An exceptionally important stress response of Pseudomonas putida strains to toxic chemicals is the induction of efflux pumps that extrude solvents, as well as other toxicants, into the surrounding medium. However, the bacterial tolerance mechanisms are still not fully understood, thus in this thesis metabolomic approaches were used to detect and identify metabolites involved in P. putida DOT-T1E tolerance to abiotic stresses, in particular focussing on the role of efflux pumps. To elucidate any metabolome alterations several strains of P. putida, including the wild type DOT-T1E, and the efflux pump knockouts DOT-T1E-PS28 and DOT-T1E-18, were challenged with different levels of propranolol. Fourier-transform infrared (FT-IR) spectroscopy, which provided a rapid, high-throughput metabolic fingerprint of P. putida strains, was used to investigate any phenotypic changes resulting from exposure to propranolol. FT-IR data illustrated phenotypic changes associated with the presence of propranolol within the cell that could be assigned to the bacterial protein components. To complement this phenotypic fingerprinting approach metabolic profiling on the same samples was performed using gas chromatography mass spectrometry (GC-MS) to identify metabolites of interest during growth of bacteria following this toxic perturbation with propranolol. GC-MS revealed significant changes in ornithine levels which can be directly linked to bacterial tolerance mechanisms, and alterations in the levels of several other metabolites which were also modified in response to propranolol exposure. Moreover, the effect of the organic solvent toluene was also investigated using the same approach. Examination of FT-IR data indicated that protein and fatty acids were the most affected components of P. putida strains due to the presence of toluene within the cell. Moreover, application of GC-MS allowed for the identification and quantification of several metabolites which were differentially produced or consumed in the presence of toluene. To investigate the role of efflux pumps in P. putida DOT-T1E, several analytical techniques were employed including Raman spectroscopy, gas and liquid chromatography to identify and quantify the level of propranolol or toluene in P. putida cells. These analyses showed that propranolol and toluene accumulated in the mutant P. putida DOT-T1E-18 (lacking the TtgABC pump) at higher levels in comparison with the levels found in the wild-type DOT-T1E and the mutant DOT-T1E-PS28 (lacking the TtgGHI pump), indicating the key role of efflux pumps in solvent tolerance. Furthermore, the effect of Mg2+ and Ca2+ on the stabilisation of the toluene tolerance of P. putida DOT-T1E strains was examined in order to elucidate whether divalent cations interact with efflux pumps or other resistant mechanisms to improve solvent tolerance. FT-IR analysis suggested that the influence of divalent cations on the stabilisation of the toluene tolerance could be due to the contribution of metal ions towards other tolerance mechanisms such as lipopolysaccharide (LPS) instead of enhancing the activity of efflux pumps. In conclusion, this thesis presents evidence that phenotypic fingerprinting and metabolic profiling approaches in combination with chemometric methods can generate valuable information on phenotypic responses occurring within microbial cultures subjected to abiotic stress.

Les travaux de cette thèse portent sur la caractérisation chimique des ambres provenant de plusieurs gisements d’âges et d’origines géographiques variés, dont certains sont inédits. Des protocoles identiques à tous les échantillons et combinant les analyses spectroscopiques (IR et RMN 13C) et chromatographiques (THM-CPG-SM) ont été appliqués, permettant d’identifier l’origine botanique des ambres et fournissant des indices pour la reconstitution des paléoenvironnements terrestres. La caractérisation chimique des gisements d’ambre du Jurassique supérieur (Kimméridgien) jusqu’au Crétacé supérieur (Santonien) du Liban, de Jordanie, du Congo, d’Equateur et de France, permet de proposer des biomarqueurs pour les résines de Cheirolepidiaceae, une famille exclusivement mésozoïque de Conifères. Une évolution des sources botaniques des résines produites durant le Mésozoïque et le Cénozoïque est alors discutée. Une production dominée par les familles de Conifères Araucariaceae et Cheirolepidiaceae est remarquée au Jurassique supérieur et Crétacé inférieur. La production au Crétacé supérieur est plutôt dominée par des Cupressaceae. Au Cénozoïque, les origines botaniques des ambres sont plus variées, et des familles d’Angiospermes sont à l’origine de nombreux gisements, dont l’ambre du Pérou produit par une Fabaceae. La production par des Conifères reste toutefois importante au Tertiaire, à l’exemple des ambres de Nouvelle-Zélande qui ont pour origine les Araucariaceae. Les données obtenues ont permis une ré-évaluation de la classification des ambres par Py-GC-MS. Ainsi, une nouvelle molécule dont la structure est inconnue encore, a été identifiée dans les chromatogrammes d’ambres de classe Ib et Ic, ajoutant un caractère discriminant entre ces deux sous-classes. Enfin, la relation âge / maturation des résines fossiles est discutée, qui dépend avant tout des conditions d’enfouissement des résines. Une large base de données moléculaires est ainsi établie pour un grand nombre de gisements d’âges et d’origines botaniques variés, qui permettra une comparaison globale dans les travaux futurs. / This work focuses on the chemical characterisation of amber from different outcrops from different localities, and varied ages. Some of these outcrops had never been studied. All the amber samples were analysed with the same analytical techniques. The combination of the data obtained from spectroscopic (IR and 13C NMR) and chromatographic (THM-GC-MS) analysis allows the identification of the botanical origin of the amber and provide some information, for the reconstruction of the palaeoenvironment. Biomarkers for the cheirolepidiaceous resins were proposed based on the chemical characterisation of different amber outcrops dating from the Upper Jurassic (Kimmeridgian) to the Upper Cretaceous (Santonian) from Lebanon, Jordan, Congo, Ecuador and France. The Cheirolepidiaceae familt was exclusively present in the Mesozoic era. Hence, the evolution of the botanical origins of the produced resins during the Mesozoic and Cenozoic eras was discussed. It seems that Araucariaceae and Cheirolepidiaceae were the dominant resin producing trees during the Upper Jurassic and the Lower Cretaceous. While, cupressaceous resiniferous plants were dominant during the Upper Cretaceous. Howerver, resins dating from the Cenozoic era, were produced by a wider variety of plants, as resiniferous families of Angiosperm intensively participated in the resin production, i.e. the Peruvian amber produced by Fabaceae. Conifer resins traces were also detected in the Tertiary, such as the amber from the Araucariaceae found in New Zealand. The obtained data allowed a re-evaluation of the classification of ambers by Py-GC-MS, leading to the discovery of a novel molecule. This molecule of an unknown structure brings a new discrimination factor between the classes Ib and Ic. Finally, the age / maturity relationship is showed to be dependent on the burial and the conservation conditions of the resins. A broad molecular database is established based a large group of amber outcrops from different ages, and having diverse botanical origins. This database could be used as a comparative platform for further work in the future.

Les menaces constantes de terrorisme nécessitent le développement d'instruments permettant de détecter efficacement des agents chimiques de guerre. L'objectif de ce travail était la réalisation d'un spectromètre de masse devant effectuer des analyses de type : LC/ESI-MS et GC/EI-MS, sur des échantillons sous tous les états : solide, liquide, gazeux et qui soit rapide. Une première partie de ce travail a consisté à étudier le fonctionnement du spectromètre de masse LTQ Velos, puis de faire une étude des modes d'injection axiale et radiale des ions par simulation à l'aide du logiciel SIMION. L'étude de l'injection radiale, nous a démontré la faisabilité de ce mode d'injection dans un piège linéaire. Ainsi, lors d'applications spécifiques dans lesquelles l'axe central doit être libéré, le mode d'activation par IRMPD peut être envisagé. Une deuxième partie de ce travail a consisté à modifier la source CI du module ETD en source EI. Trois sources EI (la Thermo, la NERMAG et la source trappe) ont été étudiées afin de déterminer celle qui serait la plus efficace et offrirait un bon compromis en terme de coût et de temps de développement. La source Thermo a été retenue et a ensuite été implémentée dans le module ETD du LTQ Velos qui a été couplé à un GC rapide pour effectuer des tests préliminaires de faisabilité de ce couplage. Ainsi, ces tests ont permis de caractériser le GC/EI-LTQ Velos comme étant capable d'effectuer des analyses en GC/MS rapide (de l'ordre de ? 5 min). Ce GC/MS rapide a ensuite été intégré dans le démonstrateur ainsi que le collecteur aérien chimique et le détecteur TIC et POC. Des essais préliminaires concluants ont été réalisés sur ce démonstrateur. / Constant threats of terrorism require the development of tools to effectively detect chemical warfare agents. The aim of this work was to develop a mass spectrometer capable of performing rapid LC/ESI-MS and GC/EI-MS analyses on samples from all states: solid, liquid and gaseous. The first part of this work was to study the principle of operation of the linear ion trap LTQ Velos, then to study axial and radial ion injection in the linear ion trap by means of computer simulation using SIMION. The feasibility of performing radial ion injection has been demonstrated, thus in specific applications in which the central axis needs to be released, the IRMPD activation mode may be considered. A second part of this work was to adapt the existing ETD module to accommodate EI. Three EI sources (the Thermo, the NERMAG and the trap source) were studied to determine which one would be the most effective and offer a good compromise in terms of cost and development time. The Thermo source has been selected and modified to conduct EI within the ETD module of the LTQ Velos which was interfaced to a fast GC (Heracles II). Preliminary tests characterized the dual pressure ion trap as a mass analyzer for performing rapid GC/MS analyses. The results showed that the GC-LIT with its high scanning speed was able to provide sufficient scans across chromatographic peaks when working in both the conventional and the fast GC modes, and further offered good EI spectral information. This GC/MS was then implemented into the demonstrator as well as the air sampler and the TIC/POC detector. Conclusive preliminary tests have been made on this demonstrator.

The normal operation of the endocrine (hormonal) system can be disrupted by a number of man-made and naturally-occurring chemicals, thereby affecting those physiological processes that are under hormonal control. Such substances are called endocrine disrupting compounds (EDCs). The endocrine disruption issue has alarmed the environmental authorities since the substances involved can hinder hormonal processes causing far-reaching effects on reproduction and development in current and future human and wildlife generations. Effects on some species of fish triggered worldwide concern and initiated a research scheme which is being undertaken by various organisations e.g. United States Environmental Protection Agency (USEPA), United Kingdom Environment Agency (UKEA), Oslo and Paris Commission (OSPAR), Japan Environment Agency (JEA) and World Wildlife Fund (WWF) in order to assess the effects (present and potential), point of generation, levels of contamination and exposure limits. The findings showed that most of the oestrogens are produced by humans and animals and get discharged into river streams mainly through sewage effluents. Fish in particular have been found to be affected the most even when the oestrogenic levels in water are very low. The probability of future European legislation to eliminate hormonally active compounds from wastewaters suggests that new and alternative methods should be developed for their removal. In this work, the adsorption of 17ß-oestradiol (E2) and 17a-ethinyl oestradiol (EE2) onto several granular activated carbons and Hypersol-Macronet hypercrosslinked polymers was investigated by batch experiments after a low level detection system had been developed using Gas Chromatography Mass Spectrometry (GC/MS). Equilibrium experiments were carried out for all adsorbents to quantify the sorption capacity for E2 and EE2. For better assessment of the sorbents performance, their physical properties such as surface area, average pore diameter and micropore volume and chemical structure were characterised by N2 adsorption experiments, scanning electron microscopy (SEM), FTIR spectroscopy, elemental analysis, sodium capacity determination, pH titration, proton binding curves and zeta potential measurements. Adsorption isotherm data were fitted to the Langmuir and Freundlich equations. Activated carbons were found to be preferable to Hypersol-Macronet hypercrosslinked polymers for adsorption purposes. The adsorption of oestrogens appears to be controlled by hydrophobic interactions. Kinetic experiments were performed with different size ranges of adsorbents at different concentrations and the results were analysed by a particle diffusion model. It was found that concentration did not seem to influence the kinetics of the oestrogen sorption whereas the particle size of the adsorbents influenced the adsorption rate of both molecules. The particle diffusion model seemed to fit the data collected for the adsorption rate of 17B-oestradiool onto the adsorbents but gave a poor fit for most of the data collected for 17a-ethinyl oestradiol.

Afin d’identifier les composés responsables de l’arôme du gin, une procédure GC-O-MS se basant sur la fréquence de détection a été développée. Elle a permis de déterminer l’intensité odorante des composés volatils. Leur qualité d’odeur a pu être définie par le développement d’une roue des odeurs utilisée pour catégoriser les descripteurs obtenus. Cette approche nous a dans un premier temps permis d’identifier les composés potentiellement importants pour l’arôme du gin. L’origine de ces composés a ensuite été déterminée par l’étude de la fraction volatile de différents « botanicals » appartenant à la recette du gin. Cette stratégie nous a permis de constater que les baies de genièvre et les graines de coriandre étaient les principaux contributeurs en composés volatils d’impact. A l’opposé, les racines d’iris, la réglisse et les amandes ont semblé n’en apporter aucun. Nous avons donc distingué les « botanicals majeurs » et les « botanicals mineurs » selon leurs apports en composés volatils d’impact. Cette hypothèse a été globalement validée par différents tests sensoriels sur des mélanges de distillats. Enfin, une stratégie de recombinaison a été proposée dans le but de valider une sélection des composés d’impact. Une approche multicritères (intensité odorante, qualité d’odeur, propriétés physico-chimiques…) a abouti à la création de plusieurs recombinaisons. Celles-ci ont ensuite été analysées sensoriellement grâce à un test de tri-libre qui a permis de déterminer leur proximité avec le gin cible ainsi que les distances entre elles. Ainsi, une quinzaine de composés ont pu être identifiés comme influençant de manière importante la qualité aromatique du gin / In order to identify the compounds responsible for gin aroma, a GCO-MS procedure based on detection frequency analysis has been developed. It allowed the determination of volatile compound odorant intensity. Their odor quality has been defined thanks to a developed aroma wheel, used to categorize the obtained descriptors. This approach permitted the identification of gin aroma potential impact compounds. The origin of these compounds has then been determined by studying the different botanicals involved in the gin recipe. The obtained results showed that juniper berries and coriander seeds were the main contributors in terms of volatile impact compounds. At the opposite, orris roots, liquorice and almond did not seem to provide any of them. We thus differentiated the “major botanicals” from the “minor botanicals” according to their supply in volatile impact compounds. This hypothesis has been globally validated by different sensory tests on botanical distillate mixtures. Finally, a recombination procedure has been proposed in order to validate a selection of impact compounds. A multicriteria approach (odor intensity, odor quality, physic-chemical properties…) led to the creation of several recombinates. They have been sensorially analyzed by a free sorting task, which allowed determining their proximity with the target gin and the distance between them. Thus, around fifteen compounds have been identified as key compounds for gin aroma

Today, over 15,000 Ion Mobility Spectrometry (IMS) analyzers are employed at worldwide security checkpoints to detect explosives and illicit drugs. Current portal IMS instruments and other electronic nose technologies detect explosives and drugs by analyzing samples containing the headspace air and loose particles residing on a surface. Canines can outperform these systems at sampling and detecting the low vapor pressure explosives and drugs, such as RDX, PETN, cocaine, and MDMA, because these biological detectors target the volatile signature compounds available in the headspace rather than the non-volatile parent compounds of explosives and drugs. In this dissertation research volatile signature compounds available in the headspace over explosive and drug samples were detected using SPME as a headspace sampling tool coupled to an IMS analyzer. A Genetic Algorithm (GA) technique was developed to optimize the operating conditions of a commercial IMS (GE Itemizer 2), leading to the successful detection of plastic explosives (Detasheet, Semtex H, and C-4) and illicit drugs (cocaine, MDMA, and marijuana). Short sampling times (between 10 sec to 5 min) were adequate to extract and preconcentrate sufficient analytes (> 20 ng) representing the volatile signatures in the headspace of a 15 mL glass vial or a quart-sized can containing ≤ 1 g of the bulk explosive or drug. Furthermore, a research grade IMS with flexibility for changing operating conditions and physical configurations was designed and fabricated to accommodate future research into different analytes or physical configurations. The design and construction of the FIU-IMS were facilitated by computer modeling and simulation of ion’s behavior within an IMS. The simulation method developed uses SIMION/SDS and was evaluated with experimental data collected using a commercial IMS (PCP Phemto Chem 110). The FIU-IMS instrument has comparable performance to the GE Itemizer 2 (average resolving power of 14, resolution of 3 between two drugs and two explosives, and LODs range from 0.7 to 9 ng). The results from this dissertation further advance the concept of targeting volatile components to presumptively detect the presence of concealed bulk explosives and drugs by SPME-IMS, and the new FIU-IMS provides a flexible platform for future IMS research projects.

Cette thèse porte sur la dégradation photochimique des résines naturelles utilisées dans la fabrication de vernis à tableaux. Différentes résines ont été choisies pour notre étude : la sandaraque, le copal de Manille, la colophane, le mastic et la dammar. Des vernis à tableaux ont été fabriqués à partir de ces résines dissoutes dans de l’alcool, de l’huile ou de l’essence de térébenthine selon d’anciennes recettes. Ils ont par la suite été vieillis artificiellement en enceinte d’irradiation. L’étude en spectrométrie infrarouge a permis de montrer qu’une identification du type de résine était possible par cette technique. De nombreuses bandes d’absorption spécifiques ont été mises en évidence mais tendent à disparaître tout au long du photovieillissement. Néanmoins, la bande des CH (2850-3050 cm-1) permet de séparer les résines diterpéniques et triterpéniques, et l’analyse en composante principale des données permet d’affiner les identifications. Les analyses en CPG-SM nous ont permis d’identifier la plupart des molécules présentes au sein de nos vernis grâce à l’étude des fragmentations en spectrométrie de masse. Dans ce cadre, une étude poussée du comportement des molécules a été effectuée, notamment par des expériences en SM/SM. Quatre phénomènes de photodégradation ont été observés : l’isomérisation, la scission, l’hydroxylation et l’oxydation de type Norrish I des terpènes présents. Le choix du solvant utilisé dans la fabrication du vernis influence fortement la composition du vernis et sa cinétique de dégradation, en particulier dans le cas d’un vernis à l’huile. La présence d’une vitre devant le vernis a également une influence, plus ou moins importante, sur les mécanismes photochimiques. Des vernis anciens récupérés auprès de conservateurs-restaurateurs ont été identifiés grâce à la base de données effectuée à partir de nos expérimentations, validant notre méthodologie. Les premiers essais de polymères à empreinte moléculaire ont également été effectués donnant des résultats encourageants pour l’étude de mélanges de terpènes / This thesis presents a study on the photochemical degradation of natural resins used in the manufacture of painting varnishes. Following the literature, five resins were chosen for our experiments: sandarac, Manila copal, colophony, mastic and dammar. Varnishes were made from those resins dissolved in alcohol, oil or turpentine spirit, as found in old recipes. They were then photo-aged by irradiation under artificial light. The study by infrared spectrometry enabled the identification of the type of resin. Although various specific absorption bands were highlighted, they tend to disappear all along the photoageing process. Nevertheless, the C-H band situated between 2850 and 3050 cm-1 allows to separate diterpenic and triterpenic resins and the analysis by principal components can help the identification. Thanks to the study by GC-MS we could identify most of the molecules present in our varnishes by developing the fragmentation study in mass spectrometry. An advanced study of the molecules behaviour was done, especially by MS/MS experiments. Four photo-degradation reactions were observed: isomerisation, cleavage, hydroxylation and Norrish I oxidation of the terpenoids. The choice of the solvent used in the varnish can affect its composition and degradation kinetic, mostly for oil varnishes. Besides, a window pane placed before the varnish will influence the photochemical mechanisms. Ancient varnishes collected by conservator-restorers were analysed and identified thanks to the database elaborated from our results, validating our methodology. The first experiments of molecularly imprinted polymers were carried out with some encouraging results for the analysis of mixed terpenoids