The Critical Role of Ligand Flexibility on the Activity of Free and Immobilized Mn Superoxide Dismutase Mimics
dc.citation.title | Inorganics | |
dc.citation.volume | 1-22 | |
dc.contributor.orcid | https://orcid.org/0000-0003-3339-0239 | |
dc.contributor.orcid | https://orcid.org/0000-0002-1547-6891 | |
dc.creator | Richezzi, Micaela | |
dc.creator | Signorella, Sharon | |
dc.creator | Palopoli, Claudia | |
dc.creator | Pellegri, Nora | |
dc.creator | Hureau, Christelle | |
dc.creator | Signorella, Sandra R. | |
dc.date.accessioned | 2024-02-15T13:52:18Z | |
dc.date.available | 2024-02-15T13:52:18Z | |
dc.date.issued | 2023-08-30 | |
dc.description.abstract | In 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.fil | Fil: Richezzi, Micaela. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. | |
dc.description.fil | Fil: Signorella, Sharon. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. | |
dc.description.fil | Fil: Palopoli, Claudia. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. | |
dc.description.fil | Fil: Pellegri, Nora. Universidad Nacional de Rosario. Facultad de Ciencias Exactas, Ingeniería y Agrimensura. Instituto de Física Rosario (IFIR-CONICET); Argentina. | |
dc.description.fil | Fil: Hureau, Christelle. Université de Toulouse. Laboratoire de Chimie de Coordination (LCC-CNRS); France. | |
dc.description.fil | Fil: Signorella, Sandra R. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. | |
dc.description.sponsorship | Universidad Nacional de Rosario (UNR): PID 8002019040023UR, PIP-BIO483, PIP-BIO553 | |
dc.description.sponsorship | Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET): PIP-0852, PUE-0068 | |
dc.description.sponsorship | Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT): PICT-2019-03276 | |
dc.description.sponsorship | Centre National de la Recherche Scientifique (CNRS): PICS-07121 | |
dc.description.version | peerreviewed | |
dc.identifier.issn | 2304-6740 | |
dc.identifier.uri | https://hdl.handle.net/2133/26689 | |
dc.language.iso | en | |
dc.publisher | MDPI | |
dc.relation.publisherversion | https://doi.org/10.3390/inorganics11090359 | |
dc.relation.publisherversion | https://www.mdpi.com/2304-6740/11/9/359 | |
dc.rights | openAccess | |
dc.rights.holder | Richezzi, Micaela | |
dc.rights.holder | Signorella, Sharon | |
dc.rights.holder | Palopoli, Claudia | |
dc.rights.holder | Pellegri, Nora | |
dc.rights.holder | Hureau, Christelle | |
dc.rights.holder | Signorella, Sandra R. | |
dc.rights.holder | Universidad Nacional de Rosario | |
dc.rights.text | Attribution 4.0 International | |
dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | |
dc.subject | Mn bioinspired catalysts | |
dc.subject | Click chemistry | |
dc.subject | Encapsulation | |
dc.subject | Mesoporous silica | |
dc.subject | SOD activity | |
dc.title | The Critical Role of Ligand Flexibility on the Activity of Free and Immobilized Mn Superoxide Dismutase Mimics | |
dc.type | articulo | |
dc.type.collection | articulo | |
dc.type.version | publishedVersion |