Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435
Autor(a) principal: | |
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Data de Publicação: | 2022 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1007/s10529-022-03265-8 http://hdl.handle.net/11449/240271 |
Resumo: | Monoterpenes, such as beta-pinene, are secondary metabolites widely used in the flavors and fragrance industries and can have their structure altered to enhance their applicability, such as producing epoxides, which are used as intermediaries for pharmaceuticals. Epoxides are commonly synthesized by the use of inorganic acids as catalysts, although the acid medium induces epoxide degradation. To overcome these limitations biocatalysis is shown as an alternative. Related to, this work aimed to perform the synthesis of β-Pinene epoxide using Pseudozyma antarctica lipase B (Novozym®435) as a biocatalyst, while determining the independent variables that influence the reaction using experimental design tools. Different solvent systems were evaluated (cyclohexane, acetonitrile, ethyl acetate, and dichloromethane) until 72 h reaction time, from which ethyl acetate showed higher conversion into the epoxidized product (40% in 24 h). Under the other solvents systems, several oxidized by-products were obtained, such as ketones and aldehydes. Moreover, applying metrics of green chemistry, ethyl acetate was also corroborated as the most promising solvent, with a higher atom economy (66.8%) in comparison to the others (41.3%), and a smaller E-value (1.19). Ethyl acetate was the solvent/acyl donor of choice and had the molar ratio and percentage of biocatalyst increased, which resulted in 80% of the product after 3 h of reaction. To obtain an optimized model, four independent variables (temperature, stirring, molar ratio, percentage of biocatalyst) were evaluated using experimental design tools, Fractional Factorial Design and Central Composite Rotatable Design, with conversions ranging from 23 to 95% after 3 h. All the independent variables were statistically significant (p < 0.05) and had different degrees of impact on the conversion. Kinetic parameters of the reaction were determined using the Lineweaver–Burk model (results under 30.1 mmol for Km and 10.7 mmol.min−1 for Vmax). In conclusion, the combination of two different tools of experimental design provided the development of an optimized model for beta-Pinene epoxidation, achieving high conversion to the epoxidized product after 3 h. |
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Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435Beta-pineneBiocatalysisEpoxidationExperimental designLipaseNovozym 435Monoterpenes, such as beta-pinene, are secondary metabolites widely used in the flavors and fragrance industries and can have their structure altered to enhance their applicability, such as producing epoxides, which are used as intermediaries for pharmaceuticals. Epoxides are commonly synthesized by the use of inorganic acids as catalysts, although the acid medium induces epoxide degradation. To overcome these limitations biocatalysis is shown as an alternative. Related to, this work aimed to perform the synthesis of β-Pinene epoxide using Pseudozyma antarctica lipase B (Novozym®435) as a biocatalyst, while determining the independent variables that influence the reaction using experimental design tools. Different solvent systems were evaluated (cyclohexane, acetonitrile, ethyl acetate, and dichloromethane) until 72 h reaction time, from which ethyl acetate showed higher conversion into the epoxidized product (40% in 24 h). Under the other solvents systems, several oxidized by-products were obtained, such as ketones and aldehydes. Moreover, applying metrics of green chemistry, ethyl acetate was also corroborated as the most promising solvent, with a higher atom economy (66.8%) in comparison to the others (41.3%), and a smaller E-value (1.19). Ethyl acetate was the solvent/acyl donor of choice and had the molar ratio and percentage of biocatalyst increased, which resulted in 80% of the product after 3 h of reaction. To obtain an optimized model, four independent variables (temperature, stirring, molar ratio, percentage of biocatalyst) were evaluated using experimental design tools, Fractional Factorial Design and Central Composite Rotatable Design, with conversions ranging from 23 to 95% after 3 h. All the independent variables were statistically significant (p < 0.05) and had different degrees of impact on the conversion. Kinetic parameters of the reaction were determined using the Lineweaver–Burk model (results under 30.1 mmol for Km and 10.7 mmol.min−1 for Vmax). In conclusion, the combination of two different tools of experimental design provided the development of an optimized model for beta-Pinene epoxidation, achieving high conversion to the epoxidized product after 3 h.Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Laboratory of Natural Products and Biological Assays Natural Products and Food Department Center of Health Sciences Pharmacy Faculty Federal University of Rio de Janeiro (UFRJ), Av. Carlos Chagas Filho, N. 373, RJDepartment of Biotechnology and Bioprocess Faculty of Agricultural Sciences State University of São PauloFAPERJ: 201.511/2018CAPES: 88881.068489/2014-01FAPERJ: E-26/200.183/2019FAPERJ: E-26/202.728/2018Universidade Federal do Rio de Janeiro (UFRJ)Universidade de São Paulo (USP)Martins, Gustavo dos SantosStaudt, AmandaSutili, Felipe KorbusMalafaia, Camila Rodrigues AdãoLeal, Ivana Correa Ramos2023-03-01T20:09:24Z2023-03-01T20:09:24Z2022-07-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article867-878http://dx.doi.org/10.1007/s10529-022-03265-8Biotechnology Letters, v. 44, n. 7, p. 867-878, 2022.1573-67760141-5492http://hdl.handle.net/11449/24027110.1007/s10529-022-03265-82-s2.0-85132201713Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengBiotechnology Lettersinfo:eu-repo/semantics/openAccess2023-03-01T20:09:24Zoai:repositorio.unesp.br:11449/240271Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T23:03:01.838144Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435 |
title |
Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435 |
spellingShingle |
Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435 Martins, Gustavo dos Santos Beta-pinene Biocatalysis Epoxidation Experimental design Lipase Novozym 435 |
title_short |
Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435 |
title_full |
Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435 |
title_fullStr |
Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435 |
title_full_unstemmed |
Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435 |
title_sort |
Solvent screening, optimization and kinetic parameters of the biocatalytic epoxidation reaction of β-pinene mediated by Novozym®435 |
author |
Martins, Gustavo dos Santos |
author_facet |
Martins, Gustavo dos Santos Staudt, Amanda Sutili, Felipe Korbus Malafaia, Camila Rodrigues Adão Leal, Ivana Correa Ramos |
author_role |
author |
author2 |
Staudt, Amanda Sutili, Felipe Korbus Malafaia, Camila Rodrigues Adão Leal, Ivana Correa Ramos |
author2_role |
author author author author |
dc.contributor.none.fl_str_mv |
Universidade Federal do Rio de Janeiro (UFRJ) Universidade de São Paulo (USP) |
dc.contributor.author.fl_str_mv |
Martins, Gustavo dos Santos Staudt, Amanda Sutili, Felipe Korbus Malafaia, Camila Rodrigues Adão Leal, Ivana Correa Ramos |
dc.subject.por.fl_str_mv |
Beta-pinene Biocatalysis Epoxidation Experimental design Lipase Novozym 435 |
topic |
Beta-pinene Biocatalysis Epoxidation Experimental design Lipase Novozym 435 |
description |
Monoterpenes, such as beta-pinene, are secondary metabolites widely used in the flavors and fragrance industries and can have their structure altered to enhance their applicability, such as producing epoxides, which are used as intermediaries for pharmaceuticals. Epoxides are commonly synthesized by the use of inorganic acids as catalysts, although the acid medium induces epoxide degradation. To overcome these limitations biocatalysis is shown as an alternative. Related to, this work aimed to perform the synthesis of β-Pinene epoxide using Pseudozyma antarctica lipase B (Novozym®435) as a biocatalyst, while determining the independent variables that influence the reaction using experimental design tools. Different solvent systems were evaluated (cyclohexane, acetonitrile, ethyl acetate, and dichloromethane) until 72 h reaction time, from which ethyl acetate showed higher conversion into the epoxidized product (40% in 24 h). Under the other solvents systems, several oxidized by-products were obtained, such as ketones and aldehydes. Moreover, applying metrics of green chemistry, ethyl acetate was also corroborated as the most promising solvent, with a higher atom economy (66.8%) in comparison to the others (41.3%), and a smaller E-value (1.19). Ethyl acetate was the solvent/acyl donor of choice and had the molar ratio and percentage of biocatalyst increased, which resulted in 80% of the product after 3 h of reaction. To obtain an optimized model, four independent variables (temperature, stirring, molar ratio, percentage of biocatalyst) were evaluated using experimental design tools, Fractional Factorial Design and Central Composite Rotatable Design, with conversions ranging from 23 to 95% after 3 h. All the independent variables were statistically significant (p < 0.05) and had different degrees of impact on the conversion. Kinetic parameters of the reaction were determined using the Lineweaver–Burk model (results under 30.1 mmol for Km and 10.7 mmol.min−1 for Vmax). In conclusion, the combination of two different tools of experimental design provided the development of an optimized model for beta-Pinene epoxidation, achieving high conversion to the epoxidized product after 3 h. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-07-01 2023-03-01T20:09:24Z 2023-03-01T20:09:24Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1007/s10529-022-03265-8 Biotechnology Letters, v. 44, n. 7, p. 867-878, 2022. 1573-6776 0141-5492 http://hdl.handle.net/11449/240271 10.1007/s10529-022-03265-8 2-s2.0-85132201713 |
url |
http://dx.doi.org/10.1007/s10529-022-03265-8 http://hdl.handle.net/11449/240271 |
identifier_str_mv |
Biotechnology Letters, v. 44, n. 7, p. 867-878, 2022. 1573-6776 0141-5492 10.1007/s10529-022-03265-8 2-s2.0-85132201713 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Biotechnology Letters |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
867-878 |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
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1808129485176832000 |