The Critical Role of Ligand Flexibility on the Activity of Free and Immobilized Mn Superoxide Dismutase Mimics

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dc.citation.titleInorganics
dc.citation.volume1-22
dc.contributor.orcidhttps://orcid.org/0000-0003-3339-0239
dc.contributor.orcidhttps://orcid.org/0000-0002-1547-6891
dc.creatorRichezzi, Micaela
dc.creatorSignorella, Sharon
dc.creatorPalopoli, Claudia
dc.creatorPellegri, Nora
dc.creatorHureau, Christelle
dc.creatorSignorella, Sandra R.
dc.date.accessioned2024-02-15T13:52:18Z
dc.date.available2024-02-15T13:52:18Z
dc.date.issued2023-08-30
dc.description.abstractIn low-molecular-weight Mn superoxide dismutase (SOD) mimics, the ligand plays a key role in tuning the reactivity of the metal center with O2•−. We used three ligands differing in their donor sites, flexibility and/or charge, to compare the redox properties and SOD activity of the resulting Mn complexes: 1,3-bis[(pyridin-2-ylmethyl)(propargyl)amino]propane (pypapn), 1,3-bis(pyridin-2-ylmethyleneamino)propane (py2pn) and 1,4-bis(salicylidenamino)butane (H2salbn). These ligands afford Mn complexes that, in aqueous solution, exist as mononuclear species [Mn(II)(pypapn)(H2O)2]2+, [Mn(II)(py2pn)(H2O)2]2+ and [Mn(III)(salbn)(H2O)2]+. The relative reactivity of these compounds with O2•− at pH 7.8, [Mn(pypapn)(H2O)2]2+ > [Mn(salbn)(H2O)2]+ > [Mn(py2pn)(H2O)2]2+, is independent of the redox potential but strongly depends on the ligand flexibility which becomes a critical feature when the reaction occurs through an inner-sphere electron-transfer mechanism. Immobilization was used to isolate and protect the catalyst from dissociation or dimerization during catalysis. [Mn(pypapn)(H2O)2]2+, with the alkyne group, was covalently grafted to azide functionalized mesoporous silica through click chemistry, while [Mn(py2pn)(solv)2]2+ and [Mn(salbn)(solv)2]+ were encapsulated in SBA-15 mesoporous silica through ionic exchange. The retention or enhancement of the SOD activity and the improved stability of the covalently attached catalyst and the doubly charged complex encapsulated in the silica pores, make them suitable for use in aqueous media.
dc.description.filFil: Richezzi, Micaela. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina.
dc.description.filFil: Signorella, Sharon. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina.
dc.description.filFil: Palopoli, Claudia. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina.
dc.description.filFil: Pellegri, Nora. Universidad Nacional de Rosario. Facultad de Ciencias Exactas, Ingeniería y Agrimensura. Instituto de Física Rosario (IFIR-CONICET); Argentina.
dc.description.filFil: Hureau, Christelle. Université de Toulouse. Laboratoire de Chimie de Coordination (LCC-CNRS); France.
dc.description.filFil: Signorella, Sandra R. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina.
dc.description.sponsorshipUniversidad Nacional de Rosario (UNR): PID 8002019040023UR, PIP-BIO483, PIP-BIO553
dc.description.sponsorshipConsejo Nacional de Investigaciones Científicas y Técnicas (CONICET): PIP-0852, PUE-0068
dc.description.sponsorshipAgencia Nacional de Promoción Científica y Tecnológica (ANPCyT): PICT-2019-03276
dc.description.sponsorshipCentre National de la Recherche Scientifique (CNRS): PICS-07121
dc.description.versionpeerreviewed
dc.identifier.issn2304-6740
dc.identifier.urihttps://hdl.handle.net/2133/26689
dc.language.isoen
dc.publisherMDPI
dc.relation.publisherversionhttps://doi.org/10.3390/inorganics11090359
dc.relation.publisherversionhttps://www.mdpi.com/2304-6740/11/9/359
dc.rightsopenAccess
dc.rights.holderRichezzi, Micaela
dc.rights.holderSignorella, Sharon
dc.rights.holderPalopoli, Claudia
dc.rights.holderPellegri, Nora
dc.rights.holderHureau, Christelle
dc.rights.holderSignorella, Sandra R.
dc.rights.holderUniversidad Nacional de Rosario
dc.rights.textAttribution 4.0 International
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.subjectMn bioinspired catalysts
dc.subjectClick chemistry
dc.subjectEncapsulation
dc.subjectMesoporous silica
dc.subjectSOD activity
dc.titleThe Critical Role of Ligand Flexibility on the Activity of Free and Immobilized Mn Superoxide Dismutase Mimics
dc.typearticulo
dc.type.collectionarticulo
dc.type.versionpublishedVersion

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