Infrared multiphoton dissociation of the siderophore enterobactin and its Fe (III) complex. Influence of Fe (III) binding on dissociation kinetics and relative energetics

AD Leslie, R Daneshfar, DA Volmer - Journal of the American Society for …, 2007 - Springer
AD Leslie, R Daneshfar, DA Volmer
Journal of the American Society for Mass Spectrometry, 2007Springer
The dissociation pathways of the siderophore enterobactin and its complex with Fe (III) were
examined using infrared multiphoton dissociation (IRMPD). Under experimental conditions
(pH= 3.5), both compounds' electrospray spectra exhibited exclusively singly-charged
anions. The compositions of the dissociation products were characterized by accurate mass
measurements using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR
MS). The primary dissociation channel for both species was determined to be the loss of one …
Abstract
The dissociation pathways of the siderophore enterobactin and its complex with Fe(III) were examined using infrared multiphoton dissociation (IRMPD). Under experimental conditions (pH = 3.5), both compounds’ electrospray spectra exhibited exclusively singly-charged anions. The compositions of the dissociation products were characterized by accurate mass measurements using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The primary dissociation channel for both species was determined to be the loss of one serine group from the precursor molecules. To further investigate the influence of Fe(III) binding on the intramolecular interactions, dissociation kinetics and relative energetics for the loss of this serine group were determined using the focused radiation for gaseous multiphoton energy-transfer (FRAGMENT) method. From the kinetic data, it was found that enterobactin was ∼seven times more reactive than its Fe(III) complex over the range of laser intensities investigated. The relative activation energies, however, exhibited similar values, ∼7 kcal · mol−1. These results suggest that at pH = 3.5, Fe(III) interacts with only two of the three serine groups. The results from the present work are believed to be valuable for the characterization of novel siderophores as well as their associated metabolites and synthetic analogues.
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