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Master's Dissertation
DOI
https://doi.org/10.11606/D.46.2008.tde-19052008-112209
Document
Author
Full name
Roberto Susumu Utsunomiya
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2008
Supervisor
Committee
Andrade, Leandro Helgueira de (President)
Kato, Massuo Jorge
Raminelli, Cristiano
Title in Portuguese
Biorreciclagem de hexano e estudo de reações de óxido-redução usando plantas comestíveis
Keywords in Portuguese
Biorreciclagem
Hexano
Lipase
Oxidação
Plantas comestíveis
Abstract in Portuguese
O presente trabalho teve como objetivos principais utilizar reações enzimáticas para a degradação de resíduos de laboratório e na síntese de álcoois quirais. Na primeira parte foi realizada uma triagem de microrganismos e enzimas hidrolíticas, objetivando a biorreciclagem de hexano presente no resíduo contendo uma mistura hexano-acetato de etila. Esta mistura é largamente utilizada para purificação de compostos químicos por cromatografia líquida. O método de biorreciclagem consistiu na hidrólise enzimática do acetato de etila, viabilizando, dessa forma, a recuperação do hexano puro de forma simples e rápida, pois os produtos dessa reação são altamente solúveis na fase aquosa. Na segunda parte do trabalho, avaliamos o potencial catalítico de diversas plantas comestíveis em reações orgânicas de óxido-redução visando à síntese enantiosseletiva de álcoois quirais. As reações escolhidas, para tal propósito, foram a redução de cetonas pró-quirais e a resolução cinética de álcoois via oxidação enantiosseletiva. Em muitos casos, os enantiômeros foram obtidos, separadamente, com pureza enantiomérica de até 99% dependendo da planta utilizada como biocatalizador.
Title in English
Biorecycling of hexane and study of oxido-reduction reactions using edible plants
Keywords in English
Biorecycling
Edible plants
Hexane
Lipase
Oxidation
Abstract in English
The present work had as main goals the use of enzymatic reactions to degrade laboratory residues and to synthesize chiral alcohols. In the first part, it was carried out a screening of microorganisms and hydrolytic enzymes aiming the biorecycling of hexane from laboratory residues (a mixture of hexane-ethyl acetate). This misture is widely employed to purify chemicals by liquid chromatography. The biorecycling consists of enzymatic hydrolysis of ethyl acetate in a biphasic system. Due to the high solubility of the undesired products from this reaction in the aqueous phase, the hexane was easily recovered. To evaluate the possibility of treatment of effluents in a high amount, we carried out the biorecycling in a continuous system with tubular reactor using immobilized lipase (Novozyme 435). By the use of this system, the hydrolysis ratio was around 70% with no lost of enzyme stability along 6 hours work. In the second part of the work, we evaluated the catalytic potential of several edible plants in oxido-reduction reactions aiming the enantioselective synthesis of chiral alcohols. The chosen reactions were the reduction of prochiral ketones and the kinetic resolution by enantioselective oxidation. In several cases, depending of the plant employed as biocatalyst, the (R) or (S)- enantiomer were obtained in high enantiomeric purity (up to 99%). For example, the Arracacia xanthorrhiza B. (mandioquinha) performed an efficient enantioseletive reduction of 1-(4-bromophenyl)ethanone to the (S)-1-(4-bromophenyl)ethanol with 98% e.e. (enantiomeric excess), while the a Manihot esculenta (mandioca) gave the (R)-1-(4-bromophenyl)ethanol with 90% e.e. Some plants showed a good oxidative performance. For example, Coriandrum sativum L. (coentro) gave the quantitative oxidation of 1-(4-methyphenyl)ethanol to the 1-(4-metilphenyl)ethanona.
 
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Publishing Date
2008-06-03
 
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