AUTHOR=Costa Rafael O. , Ferreira Sarah S. , Pereira Crystiane A. , Harmer Jeffrey R. , Noble Christopher J. , Schenk Gerhard , Franco Roberto W. A. , Resende Jackson A. L. C. , Comba Peter , Roberts Asha E. , Fernandes Christiane , Horn Jr. Adolfo TITLE=A New Mixed-Valence Mn(II)Mn(III) Compound With Catalase and Superoxide Dismutase Activities JOURNAL=Frontiers in Chemistry VOLUME=6 YEAR=2018 URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2018.00491 DOI=10.3389/fchem.2018.00491 ISSN=2296-2646 ABSTRACT=

The synthesis, X-ray molecular structure, physico-chemical characterization and dual antioxidant activity (catalase and superoxide dismutase) of a new polymeric mixed valence Mn(III)Mn(II) complex, containing the ligand H2BPClNOL (N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)[(3-chloro)(2-hydroxy)] propylamine) is described. The monomeric unit is composed of a dinuclear Mn(II)Mn(III) moiety, [Mn(III)(μ-HBPClNOL)(μ-BPClNOL)Mn(II)(Cl)](ClO4)·2H2O, 1, in which the Mn ions are connected by two different bridging groups provided by two molecules of the ligand H2BPClNOL, a phenoxide and an alkoxide group. In the solid state, this mixed valence dinuclear unit is connected to its neighbors through chloro bridges. Magnetic measurements indicated the presence of ferromagnetic [J = +0.076(13) cm−1] and antiferromagnetic [J = −5.224(13) cm−1] interactions. The compound promotes O2•- dismutation in aqueous solution (IC50 = 0.370 μmol dm−3, kcat = 3.6x106 M−1 s−1). EPR studies revealed that a high-valent Mn(III)-O-Mn(IV) species is involved in the superoxide dismutation catalytic cycle. Complex 1 shows catalase activity only in the presence of a base, e.g., piperazine or triethylamine. Kinetic studies were carried out in the presence of piperazine and employing two different methods, resulting in kcat values of 0.58 ± 0.03 s−1 (detection of O2 production employing a Clark electrode) and 2.59 ± 0.12 s−1 (H2O2 consuption recorded via UV-Vis). EPR and ESI-(+)-MS studies indicate that piperazine induces the oxidation of 1, resulting in the formation of the catalytically active Mn(III)-O-Mn(IV) species.