Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase

Autores
Palopoli, Claudia Marcela; Duhayon, Carine; Tuchagues, Jean Pierre; Signorella, Sandra Rosanna
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A new diMnIII complex, Na[Mn2(5-SO3-salpentO)(μ-OAc)(μ-OMe)(H2O)]·4H2O, where 5-SO3-salpentOH = 1,5-bis(5-sulphonatosalicylidenamino)pentan-3-ol, has been prepared and characterized. ESI-mass spectrometry, paramagnetic 1H NMR, EPR and UV-visible spectroscopic studies on freshly prepared solutions of the complex in methanol and 9 : 1 methanol–water mixtures showed that the compound retains the triply bridged bis(μ-alkoxo)(μ-acetato)Mn23+ core in solution. In the 9 : 1 methanol–water mixture, slow substitution of acetate by water molecules took place, and after one month, the doubly bridged diMnIII complex, [Mn2(5-SO3-salpentO)(μ-OMe)(H2O)3]·5H2O, formed and could be characterized by X-ray diffraction analysis. In methanolic or aqueous basic media, acetate shifts from a bridging to a terminal coordination mode, affording the highly stable [Mn2(5-SO3-salpentO)(μ-OMe)(OAc)]− anion. The efficiency of the complex in disproportionating H2O2 depends on the solvent and correlates with the stability of the complex (towards metal dissociation) in each medium: basic buffer > aqueous base > water. The buffer preserves the integrity of the catalyst and the rate of O2 evolution remains essentially constant after successive additions of excess of H2O2. Turnovers as high as 3000 mol H2O2 per mol of catalyst, without significant decomposition and with an efficiency of kcat/KM = 1028 M−1 s−1, were measured for the complex in aqueous buffers of pH 11. Kinetic and spectroscopic results suggest a catalytic cycle that runs between MnIII2 and MnIV2 oxidation states, which is consistent with the low redox potential observed for the MnIII2/MnIIIMnIV couple of the catalyst in basic medium.
Fil: Palopoli, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Duhayon, Carine. Universite de Toulose - Le Mirail; Francia. Laboratoire de Chimie de Coordination; Francia
Fil: Tuchagues, Jean Pierre. Universite de Toulose - Le Mirail; Francia. Laboratoire de Chimie de Coordination; Francia
Fil: Signorella, Sandra Rosanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Materia
Mn Catalyst
Catalase Activity
Structure
Kinetics
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/6048
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/6048
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spelling Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalasePalopoli, Claudia MarcelaDuhayon, CarineTuchagues, Jean PierreSignorella, Sandra RosannaMn CatalystCatalase ActivityStructureKineticshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A new diMnIII complex, Na[Mn2(5-SO3-salpentO)(μ-OAc)(μ-OMe)(H2O)]·4H2O, where 5-SO3-salpentOH = 1,5-bis(5-sulphonatosalicylidenamino)pentan-3-ol, has been prepared and characterized. ESI-mass spectrometry, paramagnetic 1H NMR, EPR and UV-visible spectroscopic studies on freshly prepared solutions of the complex in methanol and 9 : 1 methanol–water mixtures showed that the compound retains the triply bridged bis(μ-alkoxo)(μ-acetato)Mn23+ core in solution. In the 9 : 1 methanol–water mixture, slow substitution of acetate by water molecules took place, and after one month, the doubly bridged diMnIII complex, [Mn2(5-SO3-salpentO)(μ-OMe)(H2O)3]·5H2O, formed and could be characterized by X-ray diffraction analysis. In methanolic or aqueous basic media, acetate shifts from a bridging to a terminal coordination mode, affording the highly stable [Mn2(5-SO3-salpentO)(μ-OMe)(OAc)]− anion. The efficiency of the complex in disproportionating H2O2 depends on the solvent and correlates with the stability of the complex (towards metal dissociation) in each medium: basic buffer > aqueous base > water. The buffer preserves the integrity of the catalyst and the rate of O2 evolution remains essentially constant after successive additions of excess of H2O2. Turnovers as high as 3000 mol H2O2 per mol of catalyst, without significant decomposition and with an efficiency of kcat/KM = 1028 M−1 s−1, were measured for the complex in aqueous buffers of pH 11. Kinetic and spectroscopic results suggest a catalytic cycle that runs between MnIII2 and MnIV2 oxidation states, which is consistent with the low redox potential observed for the MnIII2/MnIIIMnIV couple of the catalyst in basic medium.Fil: Palopoli, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaFil: Duhayon, Carine. Universite de Toulose - Le Mirail; Francia. Laboratoire de Chimie de Coordination; FranciaFil: Tuchagues, Jean Pierre. Universite de Toulose - Le Mirail; Francia. Laboratoire de Chimie de Coordination; FranciaFil: Signorella, Sandra Rosanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; ArgentinaRoyal Society of Chemistry2014-09info: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/11336/6048Palopoli, Claudia Marcela; Duhayon, Carine; Tuchagues, Jean Pierre; Signorella, Sandra Rosanna; Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase; Royal Society of Chemistry; Dalton Transactions; 43; 45; 9-2014; 17145-171550300-9246enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2014/DT/C4DT01907Einfo:eu-repo/semantics/altIdentifier/doi/10.1039/C4DT01907Einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:42:21Zoai:ri.conicet.gov.ar:11336/6048instacron: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:34982025-09-29 10:42:21.832CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
title Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
spellingShingle Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
Palopoli, Claudia Marcela
Mn Catalyst
Catalase Activity
Structure
Kinetics
title_short Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
title_full Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
title_fullStr Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
title_full_unstemmed Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
title_sort Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
dc.creator.none.fl_str_mv Palopoli, Claudia Marcela
Duhayon, Carine
Tuchagues, Jean Pierre
Signorella, Sandra Rosanna
author Palopoli, Claudia Marcela
author_facet Palopoli, Claudia Marcela
Duhayon, Carine
Tuchagues, Jean Pierre
Signorella, Sandra Rosanna
author_role author
author2 Duhayon, Carine
Tuchagues, Jean Pierre
Signorella, Sandra Rosanna
author2_role author
author
author
dc.subject.none.fl_str_mv Mn Catalyst
Catalase Activity
Structure
Kinetics
topic Mn Catalyst
Catalase Activity
Structure
Kinetics
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A new diMnIII complex, Na[Mn2(5-SO3-salpentO)(μ-OAc)(μ-OMe)(H2O)]·4H2O, where 5-SO3-salpentOH = 1,5-bis(5-sulphonatosalicylidenamino)pentan-3-ol, has been prepared and characterized. ESI-mass spectrometry, paramagnetic 1H NMR, EPR and UV-visible spectroscopic studies on freshly prepared solutions of the complex in methanol and 9 : 1 methanol–water mixtures showed that the compound retains the triply bridged bis(μ-alkoxo)(μ-acetato)Mn23+ core in solution. In the 9 : 1 methanol–water mixture, slow substitution of acetate by water molecules took place, and after one month, the doubly bridged diMnIII complex, [Mn2(5-SO3-salpentO)(μ-OMe)(H2O)3]·5H2O, formed and could be characterized by X-ray diffraction analysis. In methanolic or aqueous basic media, acetate shifts from a bridging to a terminal coordination mode, affording the highly stable [Mn2(5-SO3-salpentO)(μ-OMe)(OAc)]− anion. The efficiency of the complex in disproportionating H2O2 depends on the solvent and correlates with the stability of the complex (towards metal dissociation) in each medium: basic buffer > aqueous base > water. The buffer preserves the integrity of the catalyst and the rate of O2 evolution remains essentially constant after successive additions of excess of H2O2. Turnovers as high as 3000 mol H2O2 per mol of catalyst, without significant decomposition and with an efficiency of kcat/KM = 1028 M−1 s−1, were measured for the complex in aqueous buffers of pH 11. Kinetic and spectroscopic results suggest a catalytic cycle that runs between MnIII2 and MnIV2 oxidation states, which is consistent with the low redox potential observed for the MnIII2/MnIIIMnIV couple of the catalyst in basic medium.
Fil: Palopoli, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
Fil: Duhayon, Carine. Universite de Toulose - Le Mirail; Francia. Laboratoire de Chimie de Coordination; Francia
Fil: Tuchagues, Jean Pierre. Universite de Toulose - Le Mirail; Francia. Laboratoire de Chimie de Coordination; Francia
Fil: Signorella, Sandra Rosanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
description A new diMnIII complex, Na[Mn2(5-SO3-salpentO)(μ-OAc)(μ-OMe)(H2O)]·4H2O, where 5-SO3-salpentOH = 1,5-bis(5-sulphonatosalicylidenamino)pentan-3-ol, has been prepared and characterized. ESI-mass spectrometry, paramagnetic 1H NMR, EPR and UV-visible spectroscopic studies on freshly prepared solutions of the complex in methanol and 9 : 1 methanol–water mixtures showed that the compound retains the triply bridged bis(μ-alkoxo)(μ-acetato)Mn23+ core in solution. In the 9 : 1 methanol–water mixture, slow substitution of acetate by water molecules took place, and after one month, the doubly bridged diMnIII complex, [Mn2(5-SO3-salpentO)(μ-OMe)(H2O)3]·5H2O, formed and could be characterized by X-ray diffraction analysis. In methanolic or aqueous basic media, acetate shifts from a bridging to a terminal coordination mode, affording the highly stable [Mn2(5-SO3-salpentO)(μ-OMe)(OAc)]− anion. The efficiency of the complex in disproportionating H2O2 depends on the solvent and correlates with the stability of the complex (towards metal dissociation) in each medium: basic buffer > aqueous base > water. The buffer preserves the integrity of the catalyst and the rate of O2 evolution remains essentially constant after successive additions of excess of H2O2. Turnovers as high as 3000 mol H2O2 per mol of catalyst, without significant decomposition and with an efficiency of kcat/KM = 1028 M−1 s−1, were measured for the complex in aqueous buffers of pH 11. Kinetic and spectroscopic results suggest a catalytic cycle that runs between MnIII2 and MnIV2 oxidation states, which is consistent with the low redox potential observed for the MnIII2/MnIIIMnIV couple of the catalyst in basic medium.
publishDate 2014
dc.date.none.fl_str_mv 2014-09
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/11336/6048
Palopoli, Claudia Marcela; Duhayon, Carine; Tuchagues, Jean Pierre; Signorella, Sandra Rosanna; Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase; Royal Society of Chemistry; Dalton Transactions; 43; 45; 9-2014; 17145-17155
0300-9246
url http://hdl.handle.net/11336/6048
identifier_str_mv Palopoli, Claudia Marcela; Duhayon, Carine; Tuchagues, Jean Pierre; Signorella, Sandra Rosanna; Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase; Royal Society of Chemistry; Dalton Transactions; 43; 45; 9-2014; 17145-17155
0300-9246
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2014/DT/C4DT01907E
info:eu-repo/semantics/altIdentifier/doi/10.1039/C4DT01907E
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 13.070432

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