Submitted by Roberta Lorenzon (roberta.lorenzon@fgv.br) on 2011-06-01T12:14:10Z No. of bitstreams: 1 65080100020.pdf: 1461341 bytes, checksum: 821a0b027398efed81ec57d52f2a3263 (MD5) / Approved for entry into archive by Suzinei Teles Garcia Garcia(suzinei.garcia@fgv.br) on 2011-06-01T12:18:20Z (GMT) No. of bitstreams: 1 65080100020.pdf: 1461341 bytes, checksum: 821a0b027398efed81ec57d52f2a3263 (MD5) / Approved for entry into archive by Suzinei Teles Garcia Garcia(suzinei.garcia@fgv.br) on 2011-06-01T12:19:17Z (GMT) No. of bitstreams: 1 65080100020.pdf: 1461341 bytes, checksum: 821a0b027398efed81ec57d52f2a3263 (MD5) / Made available in DSpace on 2011-06-01T12:28:56Z (GMT). No. of bitstreams: 1 65080100020.pdf: 1461341 bytes, checksum: 821a0b027398efed81ec57d52f2a3263 (MD5) Previous issue date: 2010-11-08 / As perspectivas do mercado internacional de biocombustíveis colocam o Brasil como grande protagonista na difusão da utilização do etanol, produzido a partir da cana-de-açúcar, graças à sua competitividade e às crescentes preocupações relacionadas ao aquecimento global. Para que se possa conduzir esse processo, é preciso, necessariamente, cuidar da estratégia para a sustentabilidade da matriz energética brasileira, que serve de exemplo para os outros países. As constantes oscilações nos preços do etanol combustível, a carga tributária e a falta de tratamento equânime nas unidades da federação são fatores que podem ser considerados críticos para a expansão da demanda interna do etanol. Nesse sentido, as recentes modificações introduzidas na regulamentação da produção e comercialização do etanol combustível buscam a redução da volatilidade de preços, a flexibilidade na oferta do produto e a criação de ambiente que permita aos produtores de etanol a proteção do seu fluxo de caixa nos mercados futuros da BM&FBovespa. A carga tributária é fator motivador para a adulteração e para a manutenção da evasão fiscal. A evolução do tratamento tributário, independentemente da redução da carga tributária, indica que, a exemplo do que ocorre na tributação da gasolina, a centralização nos produtores, nas cooperativas e na empresa de comercialização de etanol, é o passo necessário para a redução da adulteração e da evasão fiscal que ainda são encontradas nesse segmento. / The biofuel international market perspectives put Brazil in the main role of dissemination of the use of ethanol, produced from sugar cane, thanks to its competitiveness and the increasing concern related to global warning. In order to lead this process, it is necessary to care for the sustainability of the Brazilian energy mix, which is a model for other countries. The constant price variation, the amount of taxes and its mishandling by the states can be considered critical factors for the domestic expansion of ethanol demand. In this context, the recent introduced modification in the ethanol production and trading regulation aims to reduce the price variation, to improve flexibility in the product offer, to create an environment that allows cash flow protection to the ethanol producers in the futures markets in the BM&FBovespa. The amount of taxes is a motivating factor for adulterated fuel and tax evasion. The evolution of the tax treatment, regardless the reduction in the amount of taxes, means that, as it happens with the gasoline taxation, the centralization in the producers, cooperatives and ethanol trading companies are the necessary step to reduce adulterated fuel and tax evasion that can still be found in this segment.

Ce projet de maitrise implique le développement et l’optimisation de deux méthodes utilisant la chromatographie liquide à haute performance couplée à la spectrométrie de masse en tandem (HPLC-MS/MS). L'objectif du premier projet était de séparer le plus rapidement possible, simultanément, 71 médicaments traitant la dysfonction érectile (ED) et 11 ingrédients naturels parfois retrouvés avec ces médicaments dans les échantillons suspectés d’être adultérés ou contrefaits. L'objectif du deuxième projet était de développer une méthode de dépistage permettant l'analyse rapide simultanée de 24 cannabinoïdes synthétiques et naturels pour une grande variété d'échantillons tels que les mélanges à base de plantes, des bâtons d'encens, de sérums et de cannabis. Dans les deux projets, la séparation a été réalisée en moins de 10 min et cela en utilisant une colonne C18 à noyau solide 100 x 2,1 mm avec des particules de 2,6 µm de diamètre couplée à un système MS avec trappe ionique orbitale fonctionnant en électronébulisation positive. En raison du nombre élevé de composés dans les deux méthodes et de l’émergence de nouveaux analogues sur le marché qui pourraient être présents dans les échantillons futurs, une méthode de dépistage LC-MS/MS ciblée/non-ciblée a été développée. Pour les deux projets, les limites de détection étaient sous les ng/mL et la variation de la précision et de l’exactitude étaient inférieures de 10,5%. Le taux de recouvrement à partir des échantillons réels variait entre 92 à 111%. L’innovation des méthodes LC-MS/MS développées au cours des projets est que le spectre de masse obtenu en mode balayage lors de l'acquisition, fournit une masse exacte pour tous les composés détectés et permet l'identification des composés initialement non-ciblés, comme des nouveaux analogues. Cette innovation amène une dimension supplémentaire aux méthodes traditionnellement utilisées, en permettant une analyse à haute résolution sur la masse de composés non-ciblés. / This master’s project involved the development and optimization of two rapid liquid chromatography tandem mass spectrometry (LC-MS/MS) methods. The objective of the first project was to simultaneously separate, as rapidly as possible, 71 erectile dysfunction (ED) treatment drugs and 11 natural ingredients sometimes found alongside ED drugs present in suspected adulterated or counterfeit samples. The objective of the second project was to develop a screening method allowing rapid, simultaneous analysis of 24 synthetic and natural cannabinoids for a wide variety of samples such as herbal smoking mixtures, incense sticks, serums and Cannabis plant material. In both projects, the separations were achieved in ≤ 10 min using 2.6 µm fused-core C18 particles packed into a 100 x 2.1 mm column coupled to an LTQ Orbitrap XL mass spectrometer operated in positive electrospray mode. Because of the very high number of compounds in both methods and the knowledge that future analogues are always immerging on the market that could thus be present in samples, a targeted/untargeted LC-MS/MS screening method was developed. For both projects, detection limits were in the sub ng/mL range and intra- and inter-assay precisions were below 10.5%. Recovery from real samples ranged from 92 to 111%. The innovation of the developed LC-MS/MS methods is that the full scan event in the MS acquisition provides accurate masses for all detected species and thus allows post-analysis identification of initially untargeted compounds, i.e., the immerging analogues. This innovation adds an additional dimension to traditional MS/MS methods, allowing high mass resolution of untargeted compounds.