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6CCVD Research

Electrochemical and Solution Structural Characterization of Fe(III) Azotochelin Complexes - Examining the Coordination Behavior of a Tetradentate Siderophore

At a Glance

Section titled ā€œAt a Glanceā€
MetadataDetails
Publication Date2022-10-17
JournalInorganic Chemistry
AuthorsNatalia G. Baranska, Alison Parkin, Anneā€Kathrin Duhmeā€Klair
InstitutionsUniversity of York
Citations3

Abstract

Section titled ā€œAbstractā€

We report an electrochemical setup comprising a boron-doped diamond (BDD) working electrode for the electrochemical study of iron(III) catecholate siderophores. We demonstrate its successful application in the voltammetric investigation of iron(III) azotochelin, an iron complex of a bis(catecholate) siderophore. Cyclic voltammetry results, when complemented by UV-vis and native electrospray ionization-mass spectrometry (ESI-MS) characterization, reveal the formation of a coordinatively unsaturated tetracoordinate 1:1 complex of Fe:azotochelin (M<sub>1</sub>:L<sub>1</sub>) at neutral pH, contrary to iron(III) tetradentate siderophore complexes of other classes which favor the hexacoordinate environment of an M<sub>2</sub>:L<sub>3</sub> species. A notable effect of pH and buffer composition on the reduction potential of iron(III) azotochelin is demonstrated. Lower pH values and buffers encompassing primary or secondary amines facilitate a positive potential shift of up to +290 mV and +250 mV vs Ag/AgCl 3 M NaCl, respectively. The study was extended to the investigation of the iron(III) complexes of hexadentate siderophores. For tris(catecholate) siderophores, enterobactin and protochelin, the reduction potentials were found to lie beyond the potential window accessible to the BDD electrode; however, we were successful in observing the electrochemical behavior of a tris(hydroxamate) siderophore, ferricrocin.

Tech Support

Section titled ā€œTech Supportā€

Original Source

Section titled ā€œOriginal Sourceā€

References

Section titled ā€œReferencesā€
  1. 2001 - The Biological Chemistry of the Elements: The Inorganic Chemistry of Life [Crossref]

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