Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study

Autores
Diaz, Mario Guillermo; Vega Hissi, Esteban Gabriel; Andrada, Matias Fernando; Garro Martinez, Juan Ceferino
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We study potential scavenging of hydrogen peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, two garlic components. The antioxidant properties of garlic are attributed to organosulfide compounds, which react with reactive oxygen species preventing the oxidative stress. We used the B3LYP functional for structure analysis and M06-2X functional for the reactions employing gaseous, aqueous and non-polar environments. The conformational analysis and Fukui functions allowed the selection of the initial structures and the region of nucleophilic attack by hydrogen peroxide. The scavenging reactions analyzed are: 1) Sulfoxidation; 2) Epoxidation; and 3) Hydrogenation. Through the intrinsic reaction coordinate, the energy profile, the activation energies, the rate constant and its temperature-dependence were calculated. The results predict that reactions occur slowly and hydrogenation is not a feasible process. Finally, the sulfoxidation of Allyl Methyl Sulfide and Diallyl Sulfide resulted to be more thermodynamically and kinetically favorable than epoxidation (rate constant values, 10−10 s−1, in comparison with 10−18 s−1 from epoxidation), becoming the most probable pathway for hydrogen peroxide scavenging.
Fil: Diaz, Mario Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Fil: Vega Hissi, Esteban Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Fil: Andrada, Matias Fernando. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Garro Martinez, Juan Ceferino. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Materia
ALLYL METHYL SULFIDE
DENSITY FUNCTIONAL CALCULATIONS
DIALLYL SULFIDE
REACTION MECHANISMS
SCAVENGING OF HYDROGEN PEROXIDE.
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/145008
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/145008
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical StudyDiaz, Mario GuillermoVega Hissi, Esteban GabrielAndrada, Matias FernandoGarro Martinez, Juan CeferinoALLYL METHYL SULFIDEDENSITY FUNCTIONAL CALCULATIONSDIALLYL SULFIDEREACTION MECHANISMSSCAVENGING OF HYDROGEN PEROXIDE.https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We study potential scavenging of hydrogen peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, two garlic components. The antioxidant properties of garlic are attributed to organosulfide compounds, which react with reactive oxygen species preventing the oxidative stress. We used the B3LYP functional for structure analysis and M06-2X functional for the reactions employing gaseous, aqueous and non-polar environments. The conformational analysis and Fukui functions allowed the selection of the initial structures and the region of nucleophilic attack by hydrogen peroxide. The scavenging reactions analyzed are: 1) Sulfoxidation; 2) Epoxidation; and 3) Hydrogenation. Through the intrinsic reaction coordinate, the energy profile, the activation energies, the rate constant and its temperature-dependence were calculated. The results predict that reactions occur slowly and hydrogenation is not a feasible process. Finally, the sulfoxidation of Allyl Methyl Sulfide and Diallyl Sulfide resulted to be more thermodynamically and kinetically favorable than epoxidation (rate constant values, 10−10 s−1, in comparison with 10−18 s−1 from epoxidation), becoming the most probable pathway for hydrogen peroxide scavenging.Fil: Diaz, Mario Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaFil: Vega Hissi, Esteban Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaFil: Andrada, Matias Fernando. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Garro Martinez, Juan Ceferino. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaWiley Blackwell Publishing, Inc2020-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/145008Diaz, Mario Guillermo; Vega Hissi, Esteban Gabriel; Andrada, Matias Fernando; Garro Martinez, Juan Ceferino; Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study; Wiley Blackwell Publishing, Inc; ChemistrySelect; 5; 11; 3-2020; 3234-32422365-6549CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/slct.201904725info:eu-repo/semantics/altIdentifier/doi/10.1002/slct.201904725info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:57:13Zoai:ri.conicet.gov.ar:11336/145008instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 09:57:14.013CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study
title Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study
spellingShingle Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study
Diaz, Mario Guillermo
ALLYL METHYL SULFIDE
DENSITY FUNCTIONAL CALCULATIONS
DIALLYL SULFIDE
REACTION MECHANISMS
SCAVENGING OF HYDROGEN PEROXIDE.
title_short Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study
title_full Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study
title_fullStr Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study
title_full_unstemmed Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study
title_sort Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study
dc.creator.none.fl_str_mv Diaz, Mario Guillermo
Vega Hissi, Esteban Gabriel
Andrada, Matias Fernando
Garro Martinez, Juan Ceferino
author Diaz, Mario Guillermo
author_facet Diaz, Mario Guillermo
Vega Hissi, Esteban Gabriel
Andrada, Matias Fernando
Garro Martinez, Juan Ceferino
author_role author
author2 Vega Hissi, Esteban Gabriel
Andrada, Matias Fernando
Garro Martinez, Juan Ceferino
author2_role author
author
author
dc.subject.none.fl_str_mv ALLYL METHYL SULFIDE
DENSITY FUNCTIONAL CALCULATIONS
DIALLYL SULFIDE
REACTION MECHANISMS
SCAVENGING OF HYDROGEN PEROXIDE.
topic ALLYL METHYL SULFIDE
DENSITY FUNCTIONAL CALCULATIONS
DIALLYL SULFIDE
REACTION MECHANISMS
SCAVENGING OF HYDROGEN PEROXIDE.
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We study potential scavenging of hydrogen peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, two garlic components. The antioxidant properties of garlic are attributed to organosulfide compounds, which react with reactive oxygen species preventing the oxidative stress. We used the B3LYP functional for structure analysis and M06-2X functional for the reactions employing gaseous, aqueous and non-polar environments. The conformational analysis and Fukui functions allowed the selection of the initial structures and the region of nucleophilic attack by hydrogen peroxide. The scavenging reactions analyzed are: 1) Sulfoxidation; 2) Epoxidation; and 3) Hydrogenation. Through the intrinsic reaction coordinate, the energy profile, the activation energies, the rate constant and its temperature-dependence were calculated. The results predict that reactions occur slowly and hydrogenation is not a feasible process. Finally, the sulfoxidation of Allyl Methyl Sulfide and Diallyl Sulfide resulted to be more thermodynamically and kinetically favorable than epoxidation (rate constant values, 10−10 s−1, in comparison with 10−18 s−1 from epoxidation), becoming the most probable pathway for hydrogen peroxide scavenging.
Fil: Diaz, Mario Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Fil: Vega Hissi, Esteban Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Fil: Andrada, Matias Fernando. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Garro Martinez, Juan Ceferino. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
description We study potential scavenging of hydrogen peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, two garlic components. The antioxidant properties of garlic are attributed to organosulfide compounds, which react with reactive oxygen species preventing the oxidative stress. We used the B3LYP functional for structure analysis and M06-2X functional for the reactions employing gaseous, aqueous and non-polar environments. The conformational analysis and Fukui functions allowed the selection of the initial structures and the region of nucleophilic attack by hydrogen peroxide. The scavenging reactions analyzed are: 1) Sulfoxidation; 2) Epoxidation; and 3) Hydrogenation. Through the intrinsic reaction coordinate, the energy profile, the activation energies, the rate constant and its temperature-dependence were calculated. The results predict that reactions occur slowly and hydrogenation is not a feasible process. Finally, the sulfoxidation of Allyl Methyl Sulfide and Diallyl Sulfide resulted to be more thermodynamically and kinetically favorable than epoxidation (rate constant values, 10−10 s−1, in comparison with 10−18 s−1 from epoxidation), becoming the most probable pathway for hydrogen peroxide scavenging.
publishDate 2020
dc.date.none.fl_str_mv 2020-03
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/145008
Diaz, Mario Guillermo; Vega Hissi, Esteban Gabriel; Andrada, Matias Fernando; Garro Martinez, Juan Ceferino; Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study; Wiley Blackwell Publishing, Inc; ChemistrySelect; 5; 11; 3-2020; 3234-3242
2365-6549
CONICET Digital
CONICET
url http://hdl.handle.net/11336/145008
identifier_str_mv Diaz, Mario Guillermo; Vega Hissi, Esteban Gabriel; Andrada, Matias Fernando; Garro Martinez, Juan Ceferino; Scavenging of Hydrogen Peroxide by Allyl Methyl Sulfide and Diallyl Sulfide, Two Garlic Active Compounds: A Theoretical Study; Wiley Blackwell Publishing, Inc; ChemistrySelect; 5; 11; 3-2020; 3234-3242
2365-6549
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/slct.201904725
info:eu-repo/semantics/altIdentifier/doi/10.1002/slct.201904725
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley Blackwell Publishing, Inc
publisher.none.fl_str_mv Wiley Blackwell Publishing, Inc
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1842269450349314048
score 13.13397

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