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.
Subject(s)
Coordination Complexes/chemistry , Hydroxamic Acids/chemistry , Manganese/chemistry , Siderophores/chemistry , Coordination Complexes/metabolism , Deferoxamine/chemistry , Deferoxamine/metabolism , Electron Spin Resonance Spectroscopy , Hydroxamic Acids/metabolism , Lactams/chemistry , Lactams/metabolism , Magnetic Resonance Spectroscopy , Magnetics , Manganese/metabolism , Molecular Structure , Oxidation-Reduction , Putrescine/analogs & derivatives , Putrescine/chemistry , Putrescine/metabolism , Siderophores/metabolism , Spectrometry, Mass, Electrospray Ionization , Spectrophotometry , Succinates/chemistry , Succinates/metabolismABSTRACT
The Deepwater Horizon oil spill in 2010 released an unprecedented amount of oil into the ocean waters of the Gulf of Mexico. As a consequence, bioremediation by oil-degrading microbes has been a topic of increased focus. One factor limiting the rate of hydrocarbon degradation by microbial communities is the availability of necessary nutrients, including iron. The siderophores produced from two Vibrio spp. isolated from the Gulf of Mexico following the Deepwater Horizon oil spill, along with the well-studied oil-degrading microbe, Alcanivorax borkumensis SK2, are studied under iron-limiting conditions. Here we report the amphiphilic amphibactin siderophores produced by the oil-associated bacteria, Vibrio sp. S1B, Vibrio sp. S2A and Alcanivorax borkumensis SK2. These findings provide insight into oil-associating microbial iron acquisition.
