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Journal of inorganic biochemistry

Magnetic susceptibility of Mn(III) complexes of hydroxamate siderophores.


PMID 25978931

Abstract

The hydroxamate siderophores putrebactin, desferrioxamine B, and desferrioxamine E bind Mn(II) and promote the air oxidation of Mn(II) to Mn(III) at pH>7.1. The magnetic susceptibility of the manganese complexes were determined by the Evans method and the stoichiometry was probed with electrospray ionization mass spectrometry (ESIMS). The room temperature magnetic moments (μeff) for the manganese complexes of desferrioxamines B and E were 4.85 BM and 4.84 BM, respectively, consistent with a high spin, d(4), Mn(III) electronic configuration. The manganese complex of putrebactin had a magnetic moment of 4.98 BM, consistent with incomplete oxidation of Mn(II), as confirmed by X band EPR spectroscopy. Mass spectra of the Mn(III) desferrioxamine B and E complexes showed complexes at m/z 613.26 and 653.26, respectively, consistent with 1:1 complexation. Mass spectral peaks for manganese putrebactin at m/z 797.31 and 1221.41 corresponds to 1:2 and 2:3 Mn:putrebactin complexation. This study directly confirms the Mn(III) oxidation state in hydroxamate siderophore complexes.