New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species

Autores
Lazaro Martinez, Juan Manuel; Lombardo Lupano, Lucía Victoria; Piehl, Lidia Leonor; Rodríguez Castellón, Enrique; Campodallorto, Viviana
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report the performance of Co(II) and Cu(II) coordination complexes on H2O2 activation. The heterogeneous catalysts containing aliphatic amine, N-heterocycle, and/or carboxylic acid ligands in hydrogel materials coordinated with Co(II) or Cu(II) were used in this study. These complexes were characterized by solid-state NMR, X-ray photoelectron spectroscopy (XPS), and X-ray fluorescence techniques in order to quantify the superficial and bulk metal ion centers together with the aim of elucidating the ligands involved in the uptake of Co and Cu ions. The release of free radicals on H2O2 activation and the identity of reactive oxygen species were studied by spin trapping using DMPO in electron spin resonance (ESR) experiments. The Co(II) complex/H2O2 systems produced O2, anion superoxide (O2•–), and hydroxyl radical (OH•), which diffused into the solution at the time that a decrease in pH was detected. A possible catalytic mechanism would involve the Co(II)/Co(III) redox couple, according to XPS results. In the same way, the Cu(II) complex/H2O2 systems produced O2 and OH•, with evidence of Cu(II)/Cu(I) redox cycle. For these catalytic systems, there was no direct evidence of intermediary reactive species. The identity of the ligands played a crucial role in the efficiency of catalytic activation. In addition, in the absence of H2O2, the dissolved O2 was activated by most of the complexes tested, releasing only OH•.
Fil: Lazaro Martinez, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina
Fil: Lombardo Lupano, Lucía Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; Argentina
Fil: Piehl, Lidia Leonor. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Físico Matemática; Argentina
Fil: Rodríguez Castellón, Enrique. Universidad de Málaga; España
Fil: Campodallorto, Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Analítica y Fisicoquímica; Argentina
Materia
Hydrogen Peroxide
Copper Complexes
Cobalt Complexes
Reactive Oxigen Species
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:11336/47226
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/47226
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen SpeciesLazaro Martinez, Juan ManuelLombardo Lupano, Lucía VictoriaPiehl, Lidia LeonorRodríguez Castellón, EnriqueCampodallorto, VivianaHydrogen PeroxideCopper ComplexesCobalt ComplexesReactive Oxigen Specieshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report the performance of Co(II) and Cu(II) coordination complexes on H2O2 activation. The heterogeneous catalysts containing aliphatic amine, N-heterocycle, and/or carboxylic acid ligands in hydrogel materials coordinated with Co(II) or Cu(II) were used in this study. These complexes were characterized by solid-state NMR, X-ray photoelectron spectroscopy (XPS), and X-ray fluorescence techniques in order to quantify the superficial and bulk metal ion centers together with the aim of elucidating the ligands involved in the uptake of Co and Cu ions. The release of free radicals on H2O2 activation and the identity of reactive oxygen species were studied by spin trapping using DMPO in electron spin resonance (ESR) experiments. The Co(II) complex/H2O2 systems produced O2, anion superoxide (O2•–), and hydroxyl radical (OH•), which diffused into the solution at the time that a decrease in pH was detected. A possible catalytic mechanism would involve the Co(II)/Co(III) redox couple, according to XPS results. In the same way, the Cu(II) complex/H2O2 systems produced O2 and OH•, with evidence of Cu(II)/Cu(I) redox cycle. For these catalytic systems, there was no direct evidence of intermediary reactive species. The identity of the ligands played a crucial role in the efficiency of catalytic activation. In addition, in the absence of H2O2, the dissolved O2 was activated by most of the complexes tested, releasing only OH•.Fil: Lazaro Martinez, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; ArgentinaFil: Lombardo Lupano, Lucía Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; ArgentinaFil: Piehl, Lidia Leonor. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Físico Matemática; ArgentinaFil: Rodríguez Castellón, Enrique. Universidad de Málaga; EspañaFil: Campodallorto, Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Analítica y Fisicoquímica; ArgentinaAmerican Chemical Society2016-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/47226Lazaro Martinez, Juan Manuel; Lombardo Lupano, Lucía Victoria; Piehl, Lidia Leonor; Rodríguez Castellón, Enrique; Campodallorto, Viviana; New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species; American Chemical Society; Journal of Physical Chemistry C; 120; 51; 12-2016; 29332-293471932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b10957info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.6b10957info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:14:40Zoai:ri.conicet.gov.ar:11336/47226instacron: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:34982025-10-22 11:14:40.922CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species
title New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species
spellingShingle New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species
Lazaro Martinez, Juan Manuel
Hydrogen Peroxide
Copper Complexes
Cobalt Complexes
Reactive Oxigen Species
title_short New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species
title_full New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species
title_fullStr New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species
title_full_unstemmed New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species
title_sort New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species
dc.creator.none.fl_str_mv Lazaro Martinez, Juan Manuel
Lombardo Lupano, Lucía Victoria
Piehl, Lidia Leonor
Rodríguez Castellón, Enrique
Campodallorto, Viviana
author Lazaro Martinez, Juan Manuel
author_facet Lazaro Martinez, Juan Manuel
Lombardo Lupano, Lucía Victoria
Piehl, Lidia Leonor
Rodríguez Castellón, Enrique
Campodallorto, Viviana
author_role author
author2 Lombardo Lupano, Lucía Victoria
Piehl, Lidia Leonor
Rodríguez Castellón, Enrique
Campodallorto, Viviana
author2_role author
author
author
author
dc.subject.none.fl_str_mv Hydrogen Peroxide
Copper Complexes
Cobalt Complexes
Reactive Oxigen Species
topic Hydrogen Peroxide
Copper Complexes
Cobalt Complexes
Reactive Oxigen Species
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 report the performance of Co(II) and Cu(II) coordination complexes on H2O2 activation. The heterogeneous catalysts containing aliphatic amine, N-heterocycle, and/or carboxylic acid ligands in hydrogel materials coordinated with Co(II) or Cu(II) were used in this study. These complexes were characterized by solid-state NMR, X-ray photoelectron spectroscopy (XPS), and X-ray fluorescence techniques in order to quantify the superficial and bulk metal ion centers together with the aim of elucidating the ligands involved in the uptake of Co and Cu ions. The release of free radicals on H2O2 activation and the identity of reactive oxygen species were studied by spin trapping using DMPO in electron spin resonance (ESR) experiments. The Co(II) complex/H2O2 systems produced O2, anion superoxide (O2•–), and hydroxyl radical (OH•), which diffused into the solution at the time that a decrease in pH was detected. A possible catalytic mechanism would involve the Co(II)/Co(III) redox couple, according to XPS results. In the same way, the Cu(II) complex/H2O2 systems produced O2 and OH•, with evidence of Cu(II)/Cu(I) redox cycle. For these catalytic systems, there was no direct evidence of intermediary reactive species. The identity of the ligands played a crucial role in the efficiency of catalytic activation. In addition, in the absence of H2O2, the dissolved O2 was activated by most of the complexes tested, releasing only OH•.
Fil: Lazaro Martinez, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina
Fil: Lombardo Lupano, Lucía Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; Argentina
Fil: Piehl, Lidia Leonor. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Físico Matemática; Argentina
Fil: Rodríguez Castellón, Enrique. Universidad de Málaga; España
Fil: Campodallorto, Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas ; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Analítica y Fisicoquímica; Argentina
description We report the performance of Co(II) and Cu(II) coordination complexes on H2O2 activation. The heterogeneous catalysts containing aliphatic amine, N-heterocycle, and/or carboxylic acid ligands in hydrogel materials coordinated with Co(II) or Cu(II) were used in this study. These complexes were characterized by solid-state NMR, X-ray photoelectron spectroscopy (XPS), and X-ray fluorescence techniques in order to quantify the superficial and bulk metal ion centers together with the aim of elucidating the ligands involved in the uptake of Co and Cu ions. The release of free radicals on H2O2 activation and the identity of reactive oxygen species were studied by spin trapping using DMPO in electron spin resonance (ESR) experiments. The Co(II) complex/H2O2 systems produced O2, anion superoxide (O2•–), and hydroxyl radical (OH•), which diffused into the solution at the time that a decrease in pH was detected. A possible catalytic mechanism would involve the Co(II)/Co(III) redox couple, according to XPS results. In the same way, the Cu(II) complex/H2O2 systems produced O2 and OH•, with evidence of Cu(II)/Cu(I) redox cycle. For these catalytic systems, there was no direct evidence of intermediary reactive species. The identity of the ligands played a crucial role in the efficiency of catalytic activation. In addition, in the absence of H2O2, the dissolved O2 was activated by most of the complexes tested, releasing only OH•.
publishDate 2016
dc.date.none.fl_str_mv 2016-12
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/11336/47226
Lazaro Martinez, Juan Manuel; Lombardo Lupano, Lucía Victoria; Piehl, Lidia Leonor; Rodríguez Castellón, Enrique; Campodallorto, Viviana; New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species; American Chemical Society; Journal of Physical Chemistry C; 120; 51; 12-2016; 29332-29347
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/47226
identifier_str_mv Lazaro Martinez, Juan Manuel; Lombardo Lupano, Lucía Victoria; Piehl, Lidia Leonor; Rodríguez Castellón, Enrique; Campodallorto, Viviana; New Insights about the Selectivity in the Activation of Hydrogen Peroxide by Cobalt or Copper Hydrogel Heterogeneous Catalysts in the Generation of Reactive Oxygen Species; American Chemical Society; Journal of Physical Chemistry C; 120; 51; 12-2016; 29332-29347
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b10957
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.6b10957
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
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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
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score 12.982451

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