Synthesis, characterization and superoxide dismutase activity of a biomimetic Mn(III) complex covalently anchored to mesoporous silica

Abstract

A mononuclear Mn(III) complex of a clickable ligand, [Mn(hbpapn)(H₂O)₂]ClO₄·4.5H₂O, where H₂hbpapn = 1,3-bis[(2-hydroxybenzyl)(propargyl)amino]propane, has been prepared and fully characterized. The complex catalyzes the dismutation of superoxide employing a Mn(III)/Mn(IV) redox cycle, with catalytic rate constant of 3.9 × 10⁶ M^-1 s^-1 determined through the nitro blue tetrazolium photoreduction inhibition assay, in aqueous medium of pH 7.8. The alkyne function of the ligand was used for the covalent attachment of the catalyst to azide modified mesoporous silicas with different texture and morphology, through click chemistry. In these materials the catalyst is essentially linked to the inner pore walls, isolated and protected from the external medium. The hybrid materials can be recycled, and retain or improve the superoxide dismutase activity of the free catalyst with the pore size of the solid matrix playing a role on the activity of the catalyst.

Keywords: Biomimetic catalyst; Click chemistry; Mesoporous silica; Mn complex; SOD activity; Spectroscopy.