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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

BiorreduÃÃo de cetonas aromÃticas utilizando cÃlulas Ãntegras de Helianthus annuus L. (Girassol) / Bioreduction of aromatic ketones using whole cells of Helianthus annuus L. (SUNFLOWER)

Juliana Maria Oliveira de Souza 26 January 2012 (has links)
FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / O estudo da biocatÃlise tem se intensificado nos Ãltimos anos devido à busca de rotas sintÃticas alternativas para a obtenÃÃo de compostos enantiomericamente puros. A utilizaÃÃo de sementes de Helianthus annuus L. ainda nÃo foi relatada na literatura em reaÃÃes de biorreduÃÃo e diante dessa perspectiva, foram investigadas na biorreduÃÃo de cetonas aromÃticas, para a obtenÃÃo de Ãlcoois enantiomericamente puros. O teor de proteÃnas das sementes foi determinado pelos mÃtodos de Lowry e Bradford e apresentaram valores correspondentes a 10,1 g/L e 8,8 g/L, respectivamente. As reaÃÃes de biorreduÃÃo foram otimizadas utilizando acetofenona (1), e nestas foram avaliados os fatores: quantidade de biocatalisador, meio tamponante (pH), co-solvente, germinaÃÃo de sementes e extrato bruto com polivilpirrolidona (PVP). Foram obtidos boas conversÃes (56,9%) em meio aquoso e, excelentes excessos enantiÃmericos (ee), (>99,0%) com o extrato bruto enzimÃtico em PVP do enantiÃmero (S). Derivados da acetofenona, uma cetona α-halogenada e duas outras cetonas aromÃticas, α-tetralona e α-indanona, foram submetidas Ãs metodologias otimizadas de conversÃo e ee, obtendo-se bons resultados, com produÃÃo do enantiÃmero S, exceto para a 3-metÃxi-acetofenona em meio aquoso, que apresentou o isÃmero R. A quantificaÃÃo dos teores de conversÃo foi realizada por intermÃdio da construÃÃo de curvas de calibraÃÃo em CromatogrÃfo LÃquido de Alta EficiÃncia (CLAE), bem como a resoluÃÃo dos Ãlcoois quirais utilizando coluna quiral OB-H. / The study of biocatalysis has intensified in recent years due to the search for alternative synthetic routes to obtain enantiomerically pure compounds. The use of seeds of Helianthus annuus L. has not been reported in the literature and bioreduction reactions at this point of view, were investigated in the bioreduction of aromatic ketones, to obtain enantiomerically pure alcohols. The protein content of the seeds was determined by Lowry and Bradford methods and gave values corresponding to 10,1g/L and 8,8g/L, respectively. The bioreduction reactions were optimized using acetophenone (1), and these factors were evaluated: the amount of biocatalyst, using buffer (pH), co-solvent, seed germination and the crude extract with polyvinylpyrrolidone (PVP). Good conversions were obtained (56,9%) in aqueous solution and excellent enantiomeric excess (ee) (>99,0%) crude extract with the enzyme in PVP enantiomer (S). Derivatives of acetophenone, an α-halogenated ketone and two other aromatic ketones, α-tetralone and α-indanone were subjected to the methods of conversion and ee optimized to yield good results, with production of the S enantiomer, except for the 3-methoxy-acetophenone in aqueous media, which made the R isomer. Quantitation of the conversion levels were determined by the construction of calibration curves in a High Efficiency Liquid Chromatograph (HPLC) and the resolution of chiral alcohols using a chiral column OB-H.

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