Enzyme Control Over Ferric Iron Magnetostructural Properties.

Wang, Huan; Cleary, Michael B.; Lewis, Luke C.; Bacon, Jeffrey W.; Caravan, Peter; Shafaat, Hannah S.; Gale, Eric M.

Fe3 complexes in aqueous solution can exist as discrete mononuclear species or multinuclear magnetically coupled species. Stimuli‐driven change to Fe3 speciation represents a powerful mechanistic basis for magnetic resonance sensor technology, but ligand design strategies to exert precision control of aqueous Fe3 magnetostructural properties are entirely underexplored. In pursuit of this objective, we rationally designed a ligand to strongly favor a dinuclear μ‐oxo‐bridged and antiferromagnetically coupled complex, but which undergoes carboxylesterase mediated transformation to a mononuclear high‐spin Fe3 chelate resulting in substantial T1‐relaxivity increase. The data communicated demonstrate proof of concept for a novel and effective strategy to exert biochemical control over aqueous Fe3 magnetic, structural, and relaxometric properties.

MAGNETIC resonance; IRON; MAGNETIC sensors; LIGANDS (Chemistry); AQUEOUS solutions; ENZYMES

Angewandte Chemie, 2022, Vol 134, Issue 3, p1

0044-8249

Academic Journal

10.1002/ange.202114019