Insights into Second-Sphere effects on redox potentials, spectroscopic properties, and superoxide dismutase activity of manganese complexes with Schiff-Base Ligands

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dc.citation.titleACS Omegaes
dc.citation.volume4(1)es
dc.creatorPalopoli, Claudia
dc.creatorFerreyra, Joaquín
dc.creatorConte-Daban, Amandine
dc.creatorFoi, Ana
dc.creatorDoctorovich, Fabio
dc.creatorAnxolabehére-Mallart, Elodie
dc.creatorHureau, Christelle
dc.creatorSignorella, Sandra R.
dc.date.accessioned2020-12-16T00:05:49Z
dc.date.available2020-12-16T00:05:49Z
dc.date.issued2019-01-02
dc.descriptionSix 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.es
dc.description.filFil: Palopoli, Claudia. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina.es
dc.description.filFil: Ferreyra, Joaquín. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina.es
dc.description.filFil: Conte-Daban, Amandine. Université de Toulouse. Laboratoire de Chimie de Coordination (LCC-CNRS); France.es
dc.description.filFil: Foi, Ana. Universidad de Buenos Aires. Facultad de Ciencias Exactas y ́ Naturales. Departamento de Química Inorgánica, Analítica y Química Física. Instituto de Química Física de los Materiales, Medio Ambiente y Energía (INQUIMAE -CONICET); Argentina.es
dc.description.filFil: Doctorovich, Fabio. Universidad de Buenos Aires. Facultad de Ciencias Exactas y ́ Naturales. Departamento de Química Inorgánica, Analítica y Química Física. Instituto de Química Física de los Materiales, Medio Ambiente y Energía (INQUIMAE -CONICET); Argentina.es
dc.description.filFil: Anxolabehére-Mallart, Elodie. Université Paris-Diderot. Laboratoire d'Electrochimie Moleculaire (LEM - CNRS); France.es
dc.description.filFil: Hureau, Christelle. Université de Toulouse. Laboratoire de Chimie de Coordination (LCC-CNRS); France.es
dc.description.filFil: Signorella, Sandra R. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina.es
dc.description.sponsorshipUniversidad Nacional de Rosario
dc.description.sponsorshipConsejo Nacional de Investigaciones Científicas y Técnicas (CONICET): PIP 0337
dc.description.sponsorshipCentre National de la Recherche Scientifique (CNRS): PICS 07121
dc.description.sponsorshipBilateral agreement between Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) and Centre National de la Recherche Scientifique (CNRS) Res. 991/13
dc.description.sponsorshipAgencia Santafesina de Ciencia, Tecnología e Innovación (ASaCTeI): IO 2010-164-16
dc.formatapplication/pdf
dc.format.extent48-57es
dc.identifier.issn2470-1343es
dc.identifier.urihttp://hdl.handle.net/2133/19480
dc.language.isoenges
dc.publisherACSes
dc.relation.publisherversionhttps://pubs.acs.org/doi/10.1021/acsomega.8b03018es
dc.relation.publisherversionhttps://doi.org/10.1021/acsomega.8b03018es
dc.rightsopenAccesses
dc.rights.holderUniversidad Nacional de Rosarioes
dc.rights.holderPalopoli, Claudiaes
dc.rights.holderFerreyra, Joaquínes
dc.rights.holderConte-Daban, Amandinees
dc.rights.holderRichezzi, Micaelaes
dc.rights.holderFoi, Anaes
dc.rights.holderDoctorovich, Fabioes
dc.rights.holderAnxolabehére-Mallart, Elodiees
dc.rights.holderHureau, Christellees
dc.rights.holderSignorella, Sandra R.es
dc.rights.textAttribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)es
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectRedox reactionsen
dc.subjectLigandsen
dc.subjectSubstituentsen
dc.subjectElectron paramagnetic resonance spectroscopyes
dc.subjectTransition metalsen
dc.titleInsights into Second-Sphere effects on redox potentials, spectroscopic properties, and superoxide dismutase activity of manganese complexes with Schiff-Base Ligandses
dc.typearticle
dc.typeartículo
dc.typepublishedVersion
dc.type.collectionarticulo
dc.type.versionpublishedVersiones

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