Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification
Autor(a) principal: | |
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Data de Publicação: | 2014 |
Outros Autores: | , , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1371/journal.pone.0110277 http://hdl.handle.net/11449/117414 |
Resumo: | Pro-oxidant effects of phenolic compounds are usually correlated to the one-electron redox potential of the phenoxyl radicals. Here we demonstrated that, besides their oxidizability, hydrophobicity can also be a decisive factor. We found that esterification of protocatechuic acid (P0) provoked a profound influence in its pro-oxidant capacity. The esters bearing alkyl chains containing two (P2), four (P4) and seven (P7) carbons, but not the acid precursor (P0), were able to exacerbate the oxidation of trolox, alpha-tocopherol and rifampicin. This effect was also dependent on the catechol moiety, since neither gallic acid nor butyl gallate showed any pro-oxidant effects. A comparison was also made with apocynin, which is well-characterized regarding its pro-oxidant properties. P7 was more efficient than apocynin regarding co-oxidation of trolox. However, P7 was not able to co-oxidize glutathione and NADH, which are targets of the apocynin radical. A correlation was found between pro-oxidant capacity and the stability of the radicals, as suggested by the intensity of the peak current in the differential pulse voltammetry experiments. In conclusion, taking into account that hydroquinone and related moieties are frequently found in biomolecules and quinone-based chemotherapeutics, our demonstration that esters of protocatechuic acid are specific and potent co-catalysts in their oxidations may be very relevant as a pathway to exacerbate redox cycling reactions, which are usually involved in their biological and pharmacological mechanisms of action. |
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Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by EsterificationPro-oxidant effects of phenolic compounds are usually correlated to the one-electron redox potential of the phenoxyl radicals. Here we demonstrated that, besides their oxidizability, hydrophobicity can also be a decisive factor. We found that esterification of protocatechuic acid (P0) provoked a profound influence in its pro-oxidant capacity. The esters bearing alkyl chains containing two (P2), four (P4) and seven (P7) carbons, but not the acid precursor (P0), were able to exacerbate the oxidation of trolox, alpha-tocopherol and rifampicin. This effect was also dependent on the catechol moiety, since neither gallic acid nor butyl gallate showed any pro-oxidant effects. A comparison was also made with apocynin, which is well-characterized regarding its pro-oxidant properties. P7 was more efficient than apocynin regarding co-oxidation of trolox. However, P7 was not able to co-oxidize glutathione and NADH, which are targets of the apocynin radical. A correlation was found between pro-oxidant capacity and the stability of the radicals, as suggested by the intensity of the peak current in the differential pulse voltammetry experiments. In conclusion, taking into account that hydroquinone and related moieties are frequently found in biomolecules and quinone-based chemotherapeutics, our demonstration that esters of protocatechuic acid are specific and potent co-catalysts in their oxidations may be very relevant as a pathway to exacerbate redox cycling reactions, which are usually involved in their biological and pharmacological mechanisms of action.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Sao Paulo State Univ, UNESP, Fac Sci, Dept Chem, Sao Paulo, BrazilSao Paulo State Univ, UNESP, Nuclei Bioassays Ecophysiol & Biosynth Nat Prod N, Dept Organ Chem,Inst Chem, Sao Paulo, BrazilSao Paulo State Univ, UNESP, Sch Pharmaceut Sci, Dept Clin Anal, Sao Paulo, BrazilUniv Sao Paulo, Inst Chem Sao Carlos, Sao Carlos, SP, BrazilSao Paulo State Univ, UNESP, Fac Sci, Dept Chem, Sao Paulo, BrazilSao Paulo State Univ, UNESP, Nuclei Bioassays Ecophysiol & Biosynth Nat Prod N, Dept Organ Chem,Inst Chem, Sao Paulo, BrazilSao Paulo State Univ, UNESP, Sch Pharmaceut Sci, Dept Clin Anal, Sao Paulo, BrazilFAPESP: 13/08784-0FAPESP: 010/52327-5FAPESP: 11/03017-6FAPESP: 13/07600-3Public Library ScienceUniversidade Estadual Paulista (Unesp)Universidade de São Paulo (USP)Zeraik, Maria Luiza [UNESP]Petronio, Maicon S. [UNESP]Coelho, DyovaniRegasini, Luis Octavio [UNESP]Silva, Dulce Helena Siqueira [UNESP]Fonseca, Luiz Marcos da [UNESP]Machado, Sergio A. S.Bolzani, Vanderlan da Silva [UNESP]Ximenes, Valdecir F. [UNESP]2015-03-18T15:56:04Z2015-03-18T15:56:04Z2014-10-23info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article9application/pdfhttp://dx.doi.org/10.1371/journal.pone.0110277Plos One. San Francisco: Public Library Science, v. 9, n. 10, 9 p., 2014.1932-6203http://hdl.handle.net/11449/11741410.1371/journal.pone.0110277WOS:000343662800025WOS000343662800025.pdf470200490423124844840836852516730000-0002-1516-7765Web of Sciencereponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengPlos One2.7661,164info:eu-repo/semantics/openAccess2024-06-21T15:18:45Zoai:repositorio.unesp.br:11449/117414Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-06-21T15:18:45Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification |
title |
Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification |
spellingShingle |
Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification Zeraik, Maria Luiza [UNESP] |
title_short |
Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification |
title_full |
Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification |
title_fullStr |
Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification |
title_full_unstemmed |
Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification |
title_sort |
Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification |
author |
Zeraik, Maria Luiza [UNESP] |
author_facet |
Zeraik, Maria Luiza [UNESP] Petronio, Maicon S. [UNESP] Coelho, Dyovani Regasini, Luis Octavio [UNESP] Silva, Dulce Helena Siqueira [UNESP] Fonseca, Luiz Marcos da [UNESP] Machado, Sergio A. S. Bolzani, Vanderlan da Silva [UNESP] Ximenes, Valdecir F. [UNESP] |
author_role |
author |
author2 |
Petronio, Maicon S. [UNESP] Coelho, Dyovani Regasini, Luis Octavio [UNESP] Silva, Dulce Helena Siqueira [UNESP] Fonseca, Luiz Marcos da [UNESP] Machado, Sergio A. S. Bolzani, Vanderlan da Silva [UNESP] Ximenes, Valdecir F. [UNESP] |
author2_role |
author author author author author author author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) Universidade de São Paulo (USP) |
dc.contributor.author.fl_str_mv |
Zeraik, Maria Luiza [UNESP] Petronio, Maicon S. [UNESP] Coelho, Dyovani Regasini, Luis Octavio [UNESP] Silva, Dulce Helena Siqueira [UNESP] Fonseca, Luiz Marcos da [UNESP] Machado, Sergio A. S. Bolzani, Vanderlan da Silva [UNESP] Ximenes, Valdecir F. [UNESP] |
description |
Pro-oxidant effects of phenolic compounds are usually correlated to the one-electron redox potential of the phenoxyl radicals. Here we demonstrated that, besides their oxidizability, hydrophobicity can also be a decisive factor. We found that esterification of protocatechuic acid (P0) provoked a profound influence in its pro-oxidant capacity. The esters bearing alkyl chains containing two (P2), four (P4) and seven (P7) carbons, but not the acid precursor (P0), were able to exacerbate the oxidation of trolox, alpha-tocopherol and rifampicin. This effect was also dependent on the catechol moiety, since neither gallic acid nor butyl gallate showed any pro-oxidant effects. A comparison was also made with apocynin, which is well-characterized regarding its pro-oxidant properties. P7 was more efficient than apocynin regarding co-oxidation of trolox. However, P7 was not able to co-oxidize glutathione and NADH, which are targets of the apocynin radical. A correlation was found between pro-oxidant capacity and the stability of the radicals, as suggested by the intensity of the peak current in the differential pulse voltammetry experiments. In conclusion, taking into account that hydroquinone and related moieties are frequently found in biomolecules and quinone-based chemotherapeutics, our demonstration that esters of protocatechuic acid are specific and potent co-catalysts in their oxidations may be very relevant as a pathway to exacerbate redox cycling reactions, which are usually involved in their biological and pharmacological mechanisms of action. |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014-10-23 2015-03-18T15:56:04Z 2015-03-18T15:56:04Z |
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/10.1371/journal.pone.0110277 Plos One. San Francisco: Public Library Science, v. 9, n. 10, 9 p., 2014. 1932-6203 http://hdl.handle.net/11449/117414 10.1371/journal.pone.0110277 WOS:000343662800025 WOS000343662800025.pdf 4702004904231248 4484083685251673 0000-0002-1516-7765 |
url |
http://dx.doi.org/10.1371/journal.pone.0110277 http://hdl.handle.net/11449/117414 |
identifier_str_mv |
Plos One. San Francisco: Public Library Science, v. 9, n. 10, 9 p., 2014. 1932-6203 10.1371/journal.pone.0110277 WOS:000343662800025 WOS000343662800025.pdf 4702004904231248 4484083685251673 0000-0002-1516-7765 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Plos One 2.766 1,164 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
9 application/pdf |
dc.publisher.none.fl_str_mv |
Public Library Science |
publisher.none.fl_str_mv |
Public Library Science |
dc.source.none.fl_str_mv |
Web of Science reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
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UNESP |
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Repositório Institucional da UNESP |
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Repositório Institucional da UNESP |
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Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
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