Novel nanohybrid biocatalyst: application in the kinetic resolution of secondary alcohols |
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Authors: | " target="_blank">W S Galvão " target="_blank">B B Pinheiro " target="_blank">L R B Golçalves " target="_blank">M C de Mattos " target="_blank">T S Fonseca " target="_blank">T Regis " target="_blank">D Zampieri " target="_blank">J C S dos Santos " target="_blank">L S Costa " target="_blank">M A Correa " target="_blank">F Bohn P B A Fechine |
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Affiliation: | 1.Grupo de Química de Materiais Avan?ados (GQMAT) - Departamento de Química Analítica e Físico-Química,Universidade Federal do Ceará - UFC,Fortaleza,Brazil;2.Departamento de Engenharia Química, Universidade Federal do Ceará,Fortaleza,Brazil;3.Departamento de Química Organica e Inorganica, Laboratório de Biotecnologia e Síntese Organica (LABS),Universidade Federal do Ceará,Fortaleza,Brazil;4.Instituto de Engenharias e Desenvolvimento Sustentável,Universidade da Integra??o Internacional da Lusofonia Afro-Brasileira,Acarape,Brazil;5.Department of Inorganic Chemistry, Institute of Chemistry,State University of Campinas–UNICAMP,Campinas,Brazil;6.Laboratório Nacional de Nanotecnologia (LNNano),Centro Nacional de Pesquisa em Energia e Materiais (CNPEM),Campinas,Brazil;7.Departamento de Física,Universidade Federal do Rio Grande do Norte,Natal,Brazil |
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Abstract: | In this work, a nanohybrid material was developed and used for the first time to the kinetic resolution of secondary alcohols as rac-indanol, rac-1-phenylethanol (rac-1), rac-1-(3-bromophenyl)-1-ethanol (rac-2) and rac-1-(3-methylphenyl)-1-ethanol (rac-3). Chiral indanol is used as a precursor intermediate for the synthesis of enantiomeric drugs, such as (+)-Indatraline, Irindalone, Indinavir, (+)-Sertraline and Rasagiline mesylate. Chiral 1-phenylethanol is used as an ophthalmic preservative, a solvatochromic dye and an inhibitor of cholesterol absorption and as a mild floral fragrance. For this purpose, the ultrasound irradiation was used to couple APTES on the superparamagnetic nanoparticles surface. Then, the system was activated with glutaraldehyde and used as a support for immobilization of lipase from Pseudomonas fluorescens. Thermal stability analysis was performed in buffer and hexane, showing an excellent stability in buffer solution at 60 °C, holding 72% of the initial activity, even after 7 h. In hexane (40 °C), the immobilized enzyme retained 100% of activity with 693 min of half-life time at 50 °C. The high thermal stability is mainly related to the covalent bonding between enzymes and support. Immobilized lipase on magnetic support proved to be a robust biocatalyst in the kinetic resolution, leading to (S)-indanol with high selectivity (e.e.?>?99%, E?>?200) in 1.75 h at 50 °C, being reused five times without significant loss of the activity and selectivity. The kinetic resolution of rac-1, via acetylation reaction, catalyzed by lipase from Pseudomonas fluorescens immobilized on magnetic support, led to (R)-acetate with enantiomeric excess?>?99% and to the remaining (S)-alcohol with enantiomeric excess of 94%, conversion of 49% and E?>?200, after 48 h of reaction at 40 °C. Under the same reactions conditions, rac-2 and rac-3 were slightly less reactive, since the corresponding (R)-acetates were obtained with conversion values of 44%, but with high enantioselectivity (enantiomeric excesses?>?99% and E values?>?200). These results correspond to an important step in heterogeneous catalysis due to the ability to obtain important precursors for the synthesis of enantiomerically pure chiral drugs and other bioactive substances. |
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