Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-16T17:11:07Z No. of bitstreams: 1 ChristianCarvalho.pdf: 1874919 bytes, checksum: 3c4ecd041d9c80194ae2c47a229bbd6a (MD5) / Made available in DSpace on 2017-05-16T17:11:07Z (GMT). No. of bitstreams: 1 ChristianCarvalho.pdf: 1874919 bytes, checksum: 3c4ecd041d9c80194ae2c47a229bbd6a (MD5) Previous issue date: 2016-03-31 / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPQ) / The use of biodiesel/diesel mixtures out of the quality standards specified by the National Agency of Petroleum and Natural Gas and Biofuels - ANP can be harmful to the environment and automotive engines. Therefore, it is important to develop methodologies capable of certifying the commercial quality of such products. In such context, this project aims to design a low-cost sensor to the quantification of the biodiesel content in biodiesel / diesel pseudo-binary blends based on the dielectric constant as a response. Thus, pseudo-binary samples were prepared using soybean or babassu methyl biodiesel with commercial diesel. The dielectric measurements were performed using a LCR meter operating in parallel circuit. In this way, a voltage of 1.0 V, frequency ranging from 100 Hz to 2000 Hz and a pitch of 100 Hz were employed. The dielectric profile of diesel and biodiesel showed remarkable variations in the frequency range of 100-300 Hz and less intense changes in under 400 and 2000 Hz, which confirms greater system stability in this measurement range. The results obtained by ANOVA of pure soybean biodiesel, pure babassu biodiesel and diesel oil showed that there was no significant difference between data treatment at the 95% significance level, once the Fcalculate was lower than the Fcritical. The frequency of 1000 Hz was adopted in biodiesel analysis of content in diesel, as it was verified that the system had a higher stability at this frequency. The correspondent values of dielectric constant demonstrate regularity and stability as well as a precision between the values found. Observing the values of the dielectric constants as a function of the percentage of biodiesel in the diesel, it was possible to plot the correlation curve for a linear model. Finally, according to the Kruskal-Wallis test reinforces the thesis that measuring dielectric constants (K) can be used to determine the concentration of biodiesel in mineral diesel. / A utilização de misturas biodiesel/diesel fora dos padrões especificados pela Agência Nacional de Petróleo e Gás Natural e Biocombustíveis – ANP podem ser prejudiciais ao meio-ambiente e causar prejuízos aos donos de veículos automotivos. Neste sentido, torna-se necessário o desenvolvimento de novas metodologias capazes de certificar a qualidade destes produtos no Brasil. O presente trabalho teve por objetivo desenvolver um sensor de baixo custo para determinar o teor de biodiesel em misturas pseudo-binárias biodiesel/diesel, utilizando constante dielétrica como resposta. Para tanto, foram preparadas misturas utilizando biodieseis metílicos de soja e/ou babaçu e óleo diesel A comercial. As medidas dielétricas foram realizadas em um medidor LCR configurado para funcionar com o circuito em paralelo. Desta forma, foram empregadas tensão de 1,0 V, frequência de 100 Hz - 2000 Hz e um passo de 100 Hz. O perfil dielétrico do óleo diesel e dos biodieseis demonstrou variações acentuadas no intervalo de frequência de 100 - 300 Hz e alterações de menor intensidade entre as frequências de 400 a 2000 Hz, confirmando maior estabilidade do sistema nessa faixa. Os resultados obtidos por ANOVA do biodiesel de soja puro, biodiesel de babaçu puro e o óleo diesel, demostraram que não há diferença significativa entre os tratamentos ao nível de significância de 95%, visto que o Fcalculado foi menor que o Fcrítico. A frequência de 1000 Hz foi adotada nas análises do teor de biodiesel no diesel, pois verificou-se maior estabilidade do sistema nessa frequência. Os valores de constante dielétrica em questão demonstram regularidade e estabilidade, além de uma precisão entre os valores encontrados. Observando os valores das constantes dielétricas em função da porcentagem de biodiesel no diesel, foi possível traçar a curva de correlação para um modelo linear. Por fim, o teste de Kruskal-Wallis demonstrou que a tese de que as medidas constantes dielétricas (𝐾) podem vir a ser utilizadas para determinar a concentração de biodiesel no diesel mineral.

Die Systematische Toxikologische Analyse (STA) stellt auf Grund der großen Vielfalt und der ständigen Zunahme an toxikologisch relevanten Substanzen eine der größten Herausforderungen in der chemischen Analyse dar. In der vorliegenden Arbeit wurde daher die Eignung der Flüssigchromatographie in Kombination mit der Hybrid-Quadrupol-Flugzeitmassenspektrometrie (LC-QTOF-MS) für diesen Zweck untersucht. Dazu wurden eine Datenbank mit über 7360 und eine CID-Spektrenbibliothek mit mehr als 2720 toxikologisch relevanten Substanzen erstellt und geeignete Probenvorbereitungsmethoden entwickelt. Die Erprobung der Methoden erfolgte an dotierten Blut- und Haarproben. Hierbei zeigte sich, dass die Analyse im Auto-MS/MS-Modus (Messzyklen von MS- und MS/MS-Spektren) eine Identifizierung basischer Substanzen mittels CID-Spektren zwischen 0,5 und 2 ng/ml im Blut ermöglichte. Die Nachweisgrenzen der für 24 Wirkstoffe validierten Methode in Haaren lagen bei 3 bis 15 pg/mg. Die Eignung der LC-QTOF-MS zur STA von Haarproben wurde an 30 Drogentodesfällen und 60 Todesfällen mit bekannter chronischer Medikamenteneinnahme zu Lebzeiten sowie an 77 Blutproben nachgewiesen. Für die Suche nach Metaboliten wurde ein Metaboliten-Tool entwickelt. In der praktischen Anwendung auf Datenfiles von Blut- und Haarproben erwies sich das Tool als wertvolles Hilfsmittel zur Identifizierung unbekannter Peaks und zur Bestätigung von Suchergebnissen in der Datenbank. Zur automatischen Konzentrationsabschätzung identifizierter Substanzen wurde ein Tool „Estimate Concentration“ geschaffen. Die Überprüfung des Verfahrens an realen Blut- und Haarproben durch Vergleich mit HPLC-DAD- und GC-MS-Ergebnissen wies eine gute Übereinstimmung der Konzentrationen auf. Insgesamt zeigten die Untersuchungen, dass die LC-QTOF-MS zurzeit die am besten geeignete Methode für die STA darstellt. Auch bei einem erst später aufkommenden Verdacht kann eine gezielte Suche in dem bereits gemessenen Datenfile durchgeführt werden. / Due to the large variety and the steady increase of toxicologically relevant substances, systematic toxicological analysis (STA) is one of the most difficult tasks in analytical chemistry and, therefore, a steady topic of research and methodical improvement. For this reason, the suitability of liquid chromatography in combination with hybrid quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) for STA was investigated. For this purpose, a database of more than 7360 and a CID spectra library of more than 2720 toxicologically relevant substances and suitable methods for sample preparation were developed. The application was evaluated at spiked blood and hair samples. It was found that the analysis in Auto-MS/MS mode (alternating measurement cycles of MS and MS/MS spectra) allowed substance identification in blood using CID spectra between 0.5 and 2 ng/ml for basic substances. The detection limits of the validated method in hair ranged from 3 to 15 pg/mg for 24 drugs. The suitability of LC-QTOF-MS for STA was tested for hair samples from 30 drug-related death cases and from 60 death cases with known chronic medication as well as for 77 blood samples. For the search of metabolites, a metabolite tool was developed. In the practical application to data files from blood and hair samples, the tool proved to be very helpful for identification of unknown peaks and for confirmation of results obtained only from the database without CID spectra. A tool "Estimate Concentration" was created for automatic estimation of concentrations of identified substances. The application to real blood and hair samples and the comparison of the concentrations with results from HPLC-DAD and GC-MS showed good agreement. Overall, these investigations showed that LC-QTOF-MS is currently the most favorable method for STA. Because of the comprehensive registration of all substances in a sample, the data files can be checked for the presence of certain poisons even later without new measurements.