Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands
- Autores
- Palopoli, Claudia Marcela; Ferreyra, Joaquín; Conte Daban, Amandine; Richezzi, Micaela; Foi, Maria Ana; Doctorovich, Fabio; Anxolabéhère, Elodie; Hureau, Christelle; Signorella, Sandra Rosanna
- Año de publicación
- 2019
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Six Mn-Schiff base complexes, [Mn(X-salpn)]0/+ (salpn = 1,3-bis(sal-ic-ylidenamino)propane, X = H [1], 5-Cl [2], 2,5-F2 [3], 3,5-Cl2 [4], 5-NO2 [5], 3,5-(NO2)2 [6]), were synthesized and characterized in solution, and second-sphere effects on their electrochemical and spectroscopic properties were analyzed. The six complexes catalyze the dismutation of superoxide with catalytic rate constants in the range 0.65 to 1.54 × 106 M–1 s–1 obtained through the nitro blue tetrazolium photoreduction inhibition superoxide dismutases assay, in aqueous medium of pH 7.8. In solution, these compounds possess two labile solvent molecules in the axial positions favoring coordination of the highly nucleophilic O2•– to the metal center. Even complex 5, [Mn(5-(NO2)salpn) (OAc) (H2O)], with an axial acetate in the solid state, behaves as a 1:1 electrolyte in methanolic solution. Electron paramagnetic resonance and UV–vis monitoring of the reaction of [Mn(X-salpn)]0/+ with KO2 demonstrates that in diluted solutions these complexes behave as catalysts supporting several additions of excess O2•–, but at high complex concentrations (≥0.75 mM) catalyst self-inhibition occurs by the formation of a catalytically inactive dimer. The correlation of spectroscopic, electrochemical, and kinetics data suggest that second-sphere effects control the oxidation states of Mn involved in the O2•– dismutation cycle catalyzed by complexes 1–6 and modulate the strength of the Mn-substrate adduct for electron-transfer through an inner-sphere mechanism.
Fil: Palopoli, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Ferreyra, Joaquín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Conte Daban, Amandine. Université Paul Sabatier; Francia. Centre National de la Recherche Scientifique; Francia
Fil: Richezzi, Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina
Fil: Foi, Maria Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Anxolabéhère, Elodie. Centre National de la Recherche Scientifique; Francia. Université Paris Diderot - Paris 7; Francia
Fil: Hureau, Christelle. Université Paul Sabatier; Francia
Fil: Signorella, Sandra Rosanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina - Materia
-
SECOND-SPHERE EFFECTS
MANGANESE COMPLEXES
SCHIFF-BASE LIGANDS
SOD MIMICS - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/121750
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Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base LigandsPalopoli, Claudia MarcelaFerreyra, JoaquínConte Daban, AmandineRichezzi, MicaelaFoi, Maria AnaDoctorovich, FabioAnxolabéhère, ElodieHureau, ChristelleSignorella, Sandra RosannaSECOND-SPHERE EFFECTSMANGANESE COMPLEXESSCHIFF-BASE LIGANDSSOD MIMICShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Six Mn-Schiff base complexes, [Mn(X-salpn)]0/+ (salpn = 1,3-bis(sal-ic-ylidenamino)propane, X = H [1], 5-Cl [2], 2,5-F2 [3], 3,5-Cl2 [4], 5-NO2 [5], 3,5-(NO2)2 [6]), were synthesized and characterized in solution, and second-sphere effects on their electrochemical and spectroscopic properties were analyzed. The six complexes catalyze the dismutation of superoxide with catalytic rate constants in the range 0.65 to 1.54 × 106 M–1 s–1 obtained through the nitro blue tetrazolium photoreduction inhibition superoxide dismutases assay, in aqueous medium of pH 7.8. In solution, these compounds possess two labile solvent molecules in the axial positions favoring coordination of the highly nucleophilic O2•– to the metal center. Even complex 5, [Mn(5-(NO2)salpn) (OAc) (H2O)], with an axial acetate in the solid state, behaves as a 1:1 electrolyte in methanolic solution. Electron paramagnetic resonance and UV–vis monitoring of the reaction of [Mn(X-salpn)]0/+ with KO2 demonstrates that in diluted solutions these complexes behave as catalysts supporting several additions of excess O2•–, but at high complex concentrations (≥0.75 mM) catalyst self-inhibition occurs by the formation of a catalytically inactive dimer. The correlation of spectroscopic, electrochemical, and kinetics data suggest that second-sphere effects control the oxidation states of Mn involved in the O2•– dismutation cycle catalyzed by complexes 1–6 and modulate the strength of the Mn-substrate adduct for electron-transfer through an inner-sphere mechanism.Fil: Palopoli, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Ferreyra, Joaquín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Conte Daban, Amandine. Université Paul Sabatier; Francia. Centre National de la Recherche Scientifique; FranciaFil: Richezzi, Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; ArgentinaFil: Foi, Maria Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Anxolabéhère, Elodie. Centre National de la Recherche Scientifique; Francia. Université Paris Diderot - Paris 7; FranciaFil: Hureau, Christelle. Université Paul Sabatier; FranciaFil: Signorella, Sandra Rosanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaAmerican Chemical Society2019-01-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/121750Palopoli, Claudia Marcela; Ferreyra, Joaquín; Conte Daban, Amandine; Richezzi, Micaela; Foi, Maria Ana; et al.; Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands; American Chemical Society; ACS Omega; 4; 1; 2-1-2019; 48-572470-1343CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acsomega.8b03018info:eu-repo/semantics/altIdentifier/doi/10.1021/acsomega.8b03018info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6649300/info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:26:13Zoai:ri.conicet.gov.ar:11336/121750instacron: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 10:26:13.636CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands |
title |
Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands |
spellingShingle |
Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands Palopoli, Claudia Marcela SECOND-SPHERE EFFECTS MANGANESE COMPLEXES SCHIFF-BASE LIGANDS SOD MIMICS |
title_short |
Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands |
title_full |
Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands |
title_fullStr |
Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands |
title_full_unstemmed |
Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands |
title_sort |
Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands |
dc.creator.none.fl_str_mv |
Palopoli, Claudia Marcela Ferreyra, Joaquín Conte Daban, Amandine Richezzi, Micaela Foi, Maria Ana Doctorovich, Fabio Anxolabéhère, Elodie Hureau, Christelle Signorella, Sandra Rosanna |
author |
Palopoli, Claudia Marcela |
author_facet |
Palopoli, Claudia Marcela Ferreyra, Joaquín Conte Daban, Amandine Richezzi, Micaela Foi, Maria Ana Doctorovich, Fabio Anxolabéhère, Elodie Hureau, Christelle Signorella, Sandra Rosanna |
author_role |
author |
author2 |
Ferreyra, Joaquín Conte Daban, Amandine Richezzi, Micaela Foi, Maria Ana Doctorovich, Fabio Anxolabéhère, Elodie Hureau, Christelle Signorella, Sandra Rosanna |
author2_role |
author author author author author author author author |
dc.subject.none.fl_str_mv |
SECOND-SPHERE EFFECTS MANGANESE COMPLEXES SCHIFF-BASE LIGANDS SOD MIMICS |
topic |
SECOND-SPHERE EFFECTS MANGANESE COMPLEXES SCHIFF-BASE LIGANDS SOD MIMICS |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
Six Mn-Schiff base complexes, [Mn(X-salpn)]0/+ (salpn = 1,3-bis(sal-ic-ylidenamino)propane, X = H [1], 5-Cl [2], 2,5-F2 [3], 3,5-Cl2 [4], 5-NO2 [5], 3,5-(NO2)2 [6]), were synthesized and characterized in solution, and second-sphere effects on their electrochemical and spectroscopic properties were analyzed. The six complexes catalyze the dismutation of superoxide with catalytic rate constants in the range 0.65 to 1.54 × 106 M–1 s–1 obtained through the nitro blue tetrazolium photoreduction inhibition superoxide dismutases assay, in aqueous medium of pH 7.8. In solution, these compounds possess two labile solvent molecules in the axial positions favoring coordination of the highly nucleophilic O2•– to the metal center. Even complex 5, [Mn(5-(NO2)salpn) (OAc) (H2O)], with an axial acetate in the solid state, behaves as a 1:1 electrolyte in methanolic solution. Electron paramagnetic resonance and UV–vis monitoring of the reaction of [Mn(X-salpn)]0/+ with KO2 demonstrates that in diluted solutions these complexes behave as catalysts supporting several additions of excess O2•–, but at high complex concentrations (≥0.75 mM) catalyst self-inhibition occurs by the formation of a catalytically inactive dimer. The correlation of spectroscopic, electrochemical, and kinetics data suggest that second-sphere effects control the oxidation states of Mn involved in the O2•– dismutation cycle catalyzed by complexes 1–6 and modulate the strength of the Mn-substrate adduct for electron-transfer through an inner-sphere mechanism. Fil: Palopoli, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Ferreyra, Joaquín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Conte Daban, Amandine. Université Paul Sabatier; Francia. Centre National de la Recherche Scientifique; Francia Fil: Richezzi, Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Foi, Maria Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Anxolabéhère, Elodie. Centre National de la Recherche Scientifique; Francia. Université Paris Diderot - Paris 7; Francia Fil: Hureau, Christelle. Université Paul Sabatier; Francia Fil: Signorella, Sandra Rosanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina |
description |
Six Mn-Schiff base complexes, [Mn(X-salpn)]0/+ (salpn = 1,3-bis(sal-ic-ylidenamino)propane, X = H [1], 5-Cl [2], 2,5-F2 [3], 3,5-Cl2 [4], 5-NO2 [5], 3,5-(NO2)2 [6]), were synthesized and characterized in solution, and second-sphere effects on their electrochemical and spectroscopic properties were analyzed. The six complexes catalyze the dismutation of superoxide with catalytic rate constants in the range 0.65 to 1.54 × 106 M–1 s–1 obtained through the nitro blue tetrazolium photoreduction inhibition superoxide dismutases assay, in aqueous medium of pH 7.8. In solution, these compounds possess two labile solvent molecules in the axial positions favoring coordination of the highly nucleophilic O2•– to the metal center. Even complex 5, [Mn(5-(NO2)salpn) (OAc) (H2O)], with an axial acetate in the solid state, behaves as a 1:1 electrolyte in methanolic solution. Electron paramagnetic resonance and UV–vis monitoring of the reaction of [Mn(X-salpn)]0/+ with KO2 demonstrates that in diluted solutions these complexes behave as catalysts supporting several additions of excess O2•–, but at high complex concentrations (≥0.75 mM) catalyst self-inhibition occurs by the formation of a catalytically inactive dimer. The correlation of spectroscopic, electrochemical, and kinetics data suggest that second-sphere effects control the oxidation states of Mn involved in the O2•– dismutation cycle catalyzed by complexes 1–6 and modulate the strength of the Mn-substrate adduct for electron-transfer through an inner-sphere mechanism. |
publishDate |
2019 |
dc.date.none.fl_str_mv |
2019-01-02 |
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/11336/121750 Palopoli, Claudia Marcela; Ferreyra, Joaquín; Conte Daban, Amandine; Richezzi, Micaela; Foi, Maria Ana; et al.; Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands; American Chemical Society; ACS Omega; 4; 1; 2-1-2019; 48-57 2470-1343 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/121750 |
identifier_str_mv |
Palopoli, Claudia Marcela; Ferreyra, Joaquín; Conte Daban, Amandine; Richezzi, Micaela; Foi, Maria Ana; et al.; Insights into Second-Sphere Effects on Redox Potentials, Spectroscopic Properties, and Superoxide Dismutase Activity of Manganese Complexes with Schiff-Base Ligands; American Chemical Society; ACS Omega; 4; 1; 2-1-2019; 48-57 2470-1343 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://pubs.acs.org/doi/10.1021/acsomega.8b03018 info:eu-repo/semantics/altIdentifier/doi/10.1021/acsomega.8b03018 info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6649300/ |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf 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 |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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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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13.070432 |