Manganese(III) biliverdin IX dimethyl ester: A powerful catalytic scavenger of superoxide employing the Mn(III)/Mn(IV) redox couple

A manganese(III) complex of biliverdin IX dimethyl ester, {(MnBVDME)-B-III}(2), was prepared and characterized by elemental analysis, UV/vis spectroscopy, cyclic voltammetry, chronocoulometry, electrospray mass spectrometry, freezing-point depression, magnetic susceptibility, and catalytic dismuting of superoxide anion (O-2(.-)). In a dimeric conformation each trivalent manganese is bound to four pyrrolic nitrogens of one biliverdin dimethyl ester molecule and to the enolic oxygen of another molecule. This type of coordination stabilizes the +4 metal oxidation state, whereby the +3/+4 redox cycling of the manganese in aqueous medium was found to be at E-1/2 = +0.45 V vs NHE. This potential allows the Mn(III)/Mn(IV) couple to efficiently catalyze the dismutation of O-2(.-) with the catalytic rate constant of k(cat) = 5.0 x 10(7) M-1 s(-1) (concentration calculated per manganese) obtained by cytochrome c assay at pH 7.8 and 25 degreesC. The fifth coordination site of the manganese is occupied by an enolic oxygen, which precludes binding of NO., thus enhancing the specificity of the metal center toward O-2(.-). For the same reason the {(MnBVDME)-B-III}(2) is resistant to attack by H2O2. The compound also proved to be an efficient SOD mimic in vivo, facilitating the aerobic growth of SOD-deficient Escherichia coli.