Accurate mass-based analysis in human sport doping control : Application of liquid chromatography - time-of-flight mass spectrometry

Human sport doping control analysis is a complex and challenging task for anti-doping laboratories. The List of Prohibited Substances and Methods, updated annually by World Anti-Doping Agency (WADA), consists of hundreds of chemically and pharmacologically different low and high molecular weight compounds. This poses a considerable challenge for laboratories to analyze for them all in a limited amount of time from a limited sample aliquot. The continuous expansion of the Prohibited List obliges laboratories to keep their analytical methods updated and to research new available methodologies. In this thesis, an accurate mass-based analysis employing liquid chromatography - time-of-flight mass spectrometry (LC-TOFMS) was developed and validated to improve the power of doping control analysis. New analytical methods were developed utilizing the high mass accuracy and high information content obtained by TOFMS to generate comprehensive and generic screening procedures. The suitability of LC-TOFMS for comprehensive screening was demonstrated for the first time in the field with mass accuracies better than 1 mDa. Further attention was given to generic sample preparation, an essential part of screening analysis, to rationalize the whole work flow and minimize the need for several separate sample preparation methods. Utilizing both positive and negative ionization allowed the detection of almost 200 prohibited substances. Automatic data processing produced a Microsoft Excel based report highlighting the entries fulfilling the criteria of the reverse data base search (retention time (RT), mass accuracy, isotope match). The quantitative performance of LC-TOFMS was demonstrated with morphine, codeine and their intact glucuronide conjugates. After a straightforward sample preparation the compounds were analyzed directly without the need for hydrolysis, solvent transfer, evaporation or reconstitution. The hydrophilic interaction technique (HILIC) provided good chromatographic separation, which was critical for the morphine glucuronide isomers. A wide linear range (50-5000 ng/ml) with good precision (RSD<10%) and accuracy (±10%) was obtained, showing comparable or better performance to other methods used. In-source collision-induced dissociation (ISCID) allowed confirmation analysis with three diagnostic ions with a median mass accuracy of 1.08 mDa and repeatable ion ratios fulfilling WADA s identification criteria. The suitability of LC-TOFMS for screening of high molecular weight doping agents was demonstrated with plasma volume expanders (PVE), namely dextran and hydroxyethylstarch (HES). Specificity of the assay was improved, since interfering matrix compounds were removed by size exclusion chromatography (SEC). ISCID produced three characteristic ions with an excellent mean mass accuracy of 0.82 mDa at physiological concentration levels. In summary, by combining TOFMS with a proper sample preparation and chromatographic separation, the technique can be utilized extensively in doping control laboratories for comprehensive screening of chemically different low and high molecular weight compounds, for quantification of threshold substances and even for confirmation. LC-TOFMS rationalized the work flow in doping control laboratories by simplifying the screening scheme, expediting reporting and minimizing the analysis costs. Therefore LC-TOFMS can be exploited widely in doping control, and the need for several separate analysis techniques is reduced.

Emerging bioenergy business at Finnish independent industrial sawmills

Finnish forest industry is in the middle of a radical change. Deepening recession and the falling demand of woodworking industry´s traditional products have forced also sawmilling industry to find new and more fertile solutions to improve their operational preconditions. In recent years, the role of bioenergy production has often been highlighted as a part of sawmills´ business repertoire. Sawmilling produces naturally a lot of by-products (e.g. bark, sawdust, chips) which could be exploited more effectively in energy production, and this would bring more incomes or maybe even create new business opportunities for sawmills. Production of bioenergy is also supported by government´s climate and energy policies favouring renewable energy sources, public financial subsidies, and soaring prices of fossil fuels. Also the decreasing production of domestic pulp and paper industry releases a fair amount of sawmills´ by-products for other uses. However, bioenergy production as a part of sawmills´ by-product utilization has been so far researched very little from a managerial point of view. The purpose of this study was to explore the relative significance of the main bioenergy-related processes, resources and factors at Finnish independent industrial sawmills including partnerships, cooperation, customers relationships and investments, and also the future perspectives of bioenergy business at these sawmills with the help of two resource-based approaches (resource-based view, natural-resource-based view). Data of the study comprised of secondary data (e.g. literature), and primary data which was attracted from interviews directed to sawmill managers (or equivalent persons in charge of decisions regarding bioenergy production at sawmill). While a literature review and the Delphi method with two questionnaires were utilized as the methods of the study. According to the results of the study, the most significant processes related to the value chain of bioenergy business are connected to raw material availability and procurement, and customer relationships management. In addition to raw material and services, the most significant resources included factory and machinery, personnel, collaboration, and geographic location. Long-term cooperation deals were clearly valued as the most significant form of collaboration, and especially in processes connected to raw material procurement. Study results also revealed that factors related to demand, subsidies and prices had highest importance in connection with sawmills´ future bioenergy business. However, majority of the respondents required that certain preconditions connected to the above-mentioned factors should be fulfilled before they will continue their bioenergy-related investments. Generally, the answers showed a wide divergence of opinions among the respondents which may refer to sawmills´ different emphases and expectations concerning bioenergy. In other words, bioenergy is still perceived as a quite novel and risky area of business at Finnish independent industrial sawmills. These results indicate that the massive expansion of bioenergy business at private sawmills in Finland is not a self-evident truth. The blocking barriers seem to be connected mainly to demand of bioenergy and money. Respondents´ answers disseminated a growing dissatisfaction towards the policies of authorities, which don´t treat equally sawmill-based bioenergy compared to other forms of bioenergy. This proposition was boiled down in a sawmill manager´s comment: “There is a lot of bioenergy available, if they just want to make use of it.” It seems that the positive effects of government´s policies favouring the renewables are not taking effect at private sawmills. However, as there anyway seems to be a lot of potential connected to emerging bioenergy business at Finnish independent industrial sawmills, there is also a clear need for more profound future studies over this topic.

Renewable Energy and Climate Policies: Studies in the Forest and Energy Sector

‪This dissertation examines the impacts of energy and climate policies on the energy and forest sectors, focusing on the case of Finland. The thesis consists of an introduction article and four separate studies. The dissertation was motivated by the climate concern and the increasing demand of renewable energy. In particular, the renewable energy consumption and greenhouse gas emission reduction targets of the European Union were driving this work. In Finland, both forest and energy sectors are in key roles in achieving these targets. In fact, the separation between forest and energy sector is diminishing as the energy sector is utilizing increasing amounts of wood in energy production and as the forest sector is becoming more and more important energy producer.‬ ‪The objective of this dissertation is to find out and measure the impacts of climate and energy policies on the forest and energy sectors. In climate policy, the focus is on emissions trading, and in energy policy the dissertation focuses on the promotion of renewable forest-based energy use. The dissertation relies on empirical numerical models that are based on microeconomic theory. Numerical partial equilibrium mixed complementarity problem models were constructed to study the markets under scrutiny. The separate studies focus on co-firing of wood biomass and fossil fuels, liquid biofuel production in the pulp and paper industry, and the impacts of climate policy on the pulp and paper sector.‬ ‪The dissertation shows that the policies promoting wood-based energy may have have unexpected negative impacts. When feed-in tariff is imposed together with emissions trading, in some plants the production of renewable electricity might decrease as the emissions price increases. The dissertation also shows that in liquid biofuel production, investment subsidy may cause high direct policy costs and other negative impacts when compared to other policy instruments. The results of the dissertation also indicate that from the climate mitigation perspective, perfect competition is the favored wood market competition structure, at least if the emissions trading system is not global.‬ ‪In conclusion, this dissertation suggests that when promoting the use of wood biomass in energy production, the favored policy instruments are subsidies that promote directly the renewable energy production (i.e. production subsidy, renewables subsidy or feed-in premium). Also, the policy instrument should be designed to be dependent on the emissions price or on the substitute price. In addition, this dissertation shows that when planning policies to promote wood-based renewable energy, the goals of the policy scheme should be clear before decisions are made on the choice of the policy instruments.‬

La leyenda artúrica en la literatura alemana : el Parzival de Wolfram von Eschenbach

Integran este número de la revista ponencias presentadas en Studia Hispanica Medievalia VIII: Actas de las IX Jornadas Internacionales de Literatura Española Medieval, 2008, y de Homenaje al Quinto Centenario de Amadis de Gaula.

Assistência social : certificação das entidades beneficentes de assistência social

Seminário realizado pela Comissão de Legislação Participativa, em 13 de agosto de 2009.

Repatriamento de capitais

Seminário para a promoção de amplo debate sobre a conveniência e a oportunidade de promover-se o repatriamento de recursos depositados no exterior, detidos por pessoas físicas ou jurídicas, respectivamente residentes e sediadas no país, objeto dos Projetos de Lei n° 113, de 2003, de autoria do Dep. Luciano Castro, e n° 5.228, de 2005, de autoria do Dep. José Mentor.

Cidadania, mídia e política : relacionamento sociedade civil, meios de comunicação e parlamento

Seminário nacional realizado pela Comissão de Legislação Participativa com o objetivo de promover debates com a sociedade sobre questões atuais.

Juscelino Kubitschek

Apresenta a biografia de Juscelino Kubitschek. Dividido em duas partes, a primeira, com o título - Biografia concisa de JK - Sonho e glória, amor e dor -, faz um resgate histórico de toda a vida do ex-presidente, desde sua infância em Diamantina/MG, passando pela trajetória profissional como médico, político e Presidente do Brasil, até sua morte em 22 de agosto de 1976. Apresenta, ainda, frases importantes ditas por e sobre JK, que demonstram aspectos de sua personalidade e atuação. Na segunda parte traz discursos do ex-presidente como, por exemplo, o que defende a democracia e seus direitos políticos e os proferidos em ocasiões como a transferência da Capital Federal e a inauguração de Brasília. Contém também outros documentos, entre eles a entrevista do ministro Costa e Silva contra JK, o decreto de cassação do mandato e dos direitos políticos do senador Juscelino Kubitschek de Oliveira e a homenagem póstuma do deputado Tancredo Neves a JK.

Repatriamento de capitais do exterior

Seminário, realizado em 5 de junho de 2012, sobre o Projeto de Lei nº 113/2003, que dispõe sobre o repatriamento de recursos depositados no exterior, e o Projeto de Lei nº 5.228/2005, que institui anistia fiscal sobre a legalização ou repatriamento de recursos mantidos no exterior não declarados e extingue a punibilidade dos delitos a eles relativos.

Momento de criação : concepção de Brasília e do Congresso Nacional

Contém uma síntese de ideias sobre Brasília e o Congresso Nacional, com foco na Câmara dos Deputados. Tem por intenção explorar as relações entre a cidade e o edifício, de modo a discutir sobre como ambos estão estreitamente associados, a ponto de ser difícil imaginar um apartado do outro.

Orçamento público semi-impositivo para transferências voluntárias : diagnóstico, perspectivas e proposta de mudanças

Diagnóstico do modelo legal de transferências voluntárias realizadas pelo Governo Federal para os entes subnacionais, em face das recorrentes irregularidades relatadas pelos órgãos de controle. Questiona os motivos pelos quais o modelo vem sendo mantido há décadas diante da notória ineficiência. O fim da descentralização tutelada é a solução recomendada pela pesquisa.

Mídia, parlamento e violência : uma análise da CPI dos grupos de extermínio no Nordeste

Analisa a relação entre parlamento, mídia e sociedade na construção de uma democracia forte. Há dois elementos fundamentais para que uma sociedade estabeleça um Estado Democrático: a confiança e a participação cidadã. Parece paradoxal que em uma estrutura em que o voto é direto, haja problemas de confiança entre o Legislativo e os cidadãos. Focando a atuação da CPI dos Grupos de Extermínio no Nordeste, que tratou de um tema federal - a proteção dos direitos humanos em um cenário regional: o nordeste brasileiro, o estudo propõe uma reflexão sobre o papel do deputado no fortalecimento do elo entre a instituição Câmara Federal e o cidadão. A partir da análise feita nos jornais impressos de Pernambuco, indaga o papel da mídia no fechamento da conexão eleitoral, contribuindo ainda para a prestação de contas entre deputados e cidadãos. Pretende, ainda, verificar como se dá o relacionamento da mídia com os representantes populares.

Orçamento semi-impositivo para transferências voluntárias : diagnóstico, perspectivas e proposta

O estudo tem por base a monografia apresentada pelo autor no Curso de Especialização em Processo Legislativo do Centro de Formação, Treinamento e Aperfeiçoamento (CEFOR) da Câmara dos Deputados, concluído em novembro de 2009. Banca examinadora formada pelos Professores Eduardo Fernandez Silva, orientador e José Roberto Afonso, examinador.

Equalização dos recursos do MAC

Conteúdo: Média e alta complexidade ambulatorial (MAC)-- critérios alocativos dos recursos do SUS.