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Doctoral Thesis
DOI
10.11606/T.59.2011.tde-10082011-101558
Document
Author
Full name
Bruno José Gonçalves da Silva
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
Ribeirão Preto, 2011
Supervisor
Committee
Nassur, Maria Eugenia Queiroz (President)
Augusto, Fabio
Caramao, Elina Bastos
Moraes, Luiz Alberto Beraldo de
Nogueira, José Manuel Florêncio
Title in Portuguese
Desenvolvimento de métodos cromatográficos hifenados (in-tube SPME/LC-FLD e GCxGC/qMS) para análises de fármacos e agrotóxicos em amostras complexas
Keywords in Portuguese
cromatografia gasosa bidimensional abrangente
cromatografia líquida
fluoxetina
in-tube SPME
pesticidas
plasma
tomate
validação analítica
Abstract in Portuguese
As determinações, em níveis de traços, de fármacos em fluidos biológicos e de multirresíduos (contaminantes) em amostras alimentícias são de extrema importância, pois geram valiosos dados para fins, respectivamente, de monitorização terapêutica (individualização do regime de dosagem) e controle de qualidade (segurança alimentar). A demanda por métodos analíticos de alta resolução e com baixos limites de quantificação, para análises de amostras complexas, tem impulsionado a química analítica para o desenvolvimento de soluções inovadoras, destacando-se aquelas voltadas ao desenvolvimento ou avaliação de novos sistemas analíticos. Neste contexto, na primeira etapa desta tese, o sistema automatizado de microextração em fase sólida no capilar de polipirrol (in-tube PPY SPME) acoplado à cromatografia líquida com detecção fluorimétrica foi desenvolvido (lab-made) para a determinação enantiosseletiva de fluoxetina e de seu metabólito norfluoxetina em amostras de plasma, para fins de monitorização terapêutica. Na segunda etapa, o método cromatografia gasosa bidimensional abrangente acoplada à espectrometria de massas com analisador quadrupolo (GC x GC / qMS) foi padronizado e validado para análise de multirresíduos de agrotóxicos em tomates frescos, para fins de controle de qualidade. Dentre os resultados obtidos podemos destacar: na primeira etapa o ganho de seletividade da fase extratora de polipirrol, em sistema miniaturizado e automatizado de preparo de amostra, hifenado à separação cromatográfica (LC) com detecção fluorimétrica; e na segunda etapa, o incremento da resolução cromatográfica e detectabilidade do sistema de cromatografia gasosa bidimensional com detecção espectrométrica com analisador quadrupolo. As análises de amostras de plasma de pacientes em terapia com fluoxetina e de amostras de tomates comerciais comprovaram a aplicabilidade dos métodos propostos, padronizados e validados, em níveis de concentrações que incluem o intervalo terapêutico preconizado para a fluoxetina em plasma e os limites máximos de resíduos de agrotóxicos estabelecidos para a cultura de tomate.
Title in English
Development of hyphenated chromatographic methods (in-tube SPME/LC-FLD and GCxGC/MS) for analysis of drugs and pesticides in complex samples.
Keywords in English
analytical validation.
comprehensive two-dimensional gas chromatography
fluoxetine
in-tube SPME
liquid chromatography
pesticides
plasma
tomatoes
Abstract in English
Determination of trace levels of drugs in biological fluids and multiresidue (contaminants) in food samples is extremely important because this generates valuable data for therapeutic drug monitoring (individualization of dosage regimen) and quality control (food safety), respectively. Because of the demand for analytical methods with high resolution and low limits of quantification for analysis of complex samples, analytical chemistry has stimulated the development of innovative approaches, especially those aimed at developing or evaluating new analytical systems. In this context, in the first stage of this thesis the automated solid-phase microextraction capillary polypyrrole (in-tube "PPY SPME) coupled to liquid chromatography with fluorimetric detection was developed (lab-made) for enantioselective determination of fluoxetine and its metabolite norfluoxetine in plasma samples for therapeutic drug monitoring. In the second stage of this work, the GC x GC / qMS method was developed for multiresidues analysis of pesticides in fresh tomatoes for the purpose of quality control. In the first stage of the research the gain in terms of the selectivity of the polypyrrole extraction phase in hyphenated and automated system for sample preparation and chromatographic separation (LC) with fluorimetric detection is worthy of note. As for the second step, the highlight is the improvement in chromatographic resolution as well as in the detectability system of the system consisting of two-dimensional gas chromatography and spectrometric detection with quadrupole analyzer. Analyses of plasma samples from patients undergoing therapy with fluoxetine and of samples of commercially available tomatoes proved the applicability of the proposed methods, which were optimized and validated at concentrations levels that include the therapeutic range for the analyzed drugs in plasma and the maximum residue limits of pesticides for growing tomatoes.
 
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Tese.pdf (3.21 Mbytes)
Publishing Date
2011-10-27
 
WARNING: The material described below relates to works resulting from this thesis or dissertation. The contents of these works are the author's responsibility.
  • BUENO, Jordana S, SILVA, Bruno J.G, and QUEIROZ, Maria Eugênia C. Enantioselective analysis of fluoxetine and norfluoxetine in plasma samples by protein precipitation and liquid chromatography with fluorescence detection [doi:10.1590/S0103-50532011000700004]. Journal of the Brazilian Chemical Society [online], 2011, vol. 22, n. 7, p. 1221-1228.
  • SILVA, Bruno José Gonçalves, et al. Evaluation of comprehensive two-dimensional gas chromatography coupled to rapid scanning quadrupole mass spectrometry for quantitative analysis [doi:10.1016/j.chroma.2012.05.035]. Journal of Chromatography A [online], 2012, vol. 1255, p. 177-183.
  • SILVA, Bruno José Gonçalves, LANçAS, Fernando Mauro, and QUEIROZ, Maria Eugênia Costa. Determination of fluoxetine and norfluoxetine enantiomers in human plasma by polypyrrole-coated capillary in-tube solid-phase microextraction coupled with liquid chromatography-fluorescence detection [doi:10.1016/j.chroma.2009.10.034]. Journal of Chromatography A [online], 2009, vol. 1216, n. 49, p. 8590-8597.
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