title: Redox reactions of phenazine antibiotics with ferric (hydr)oxides and molecular oxygen.
abstract: Phenazines are small redox-active molecules produced by a variety of bacteria. Beyond merely serving as antibiotics, recent studies suggest that phenazines play important physiological roles, including one in iron acquisition. Here we characterize the ability of four electrochemically reduced natural phenazines--pyocyanin (PYO), phenazine-1-carboxylate (PCA), phenazine-1-carboxamide, and 1-hydroxyphenazine (1-OHPHZ)--to reductively dissolve ferrihydrite and hematite in the pH range 5-8. Generally, the reaction rate is higher for a phenazine with a lower reduction potential, with the reaction between PYO and ferrihydrite at pH 5 being an exception; the rate decreases as the pH increases; the rate is higher for poorly crystalline ferrihydrite than for highly crystalline hematite. Ferric (hydr)oxide reduction by reduced phenazines can potentially be inhibited by oxygen, where O2 competes with Fe(III) as the final oxidant The reactivity of reduced phenazines with 02 decreases in the order: PYO > 1-OHPHZ > PCA. Strikingly, reduced PYO,which isthe least reactive phenazine with ferrihydrite and hematite at pH 7, is the most reactive phenazine with O2. These results imply that different phenazines may perform different functions in environments with gradients of iron and O2.
authors.affiliation: Department of Biology, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
authors.forename: Yun
authors.initials: Y
authors.lastname: Wang
authors.forename: Dianne K
authors.initials: DK
authors.lastname: Newman
mesh_terms: D000900:Anti-Bacterial Agents / Q000737:chemistry*; D004563:Electrochemistry; D005290:Ferric Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010619:Phenazines / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000900:Anti-Bacterial Agents; D005290:Ferric Compounds; D010619:Phenazines; C000499:ferric oxide; D010100:Oxygen