Iron Gall Ink Revisited: In Situ Oxidation of Fe(II)-Tannin Complex for Fluidic-Interface Engineering

The ancient wisdom found in iron gall ink guides this work to a simple but advanced solution to the molecular engineering of fluidic interfaces. The Fe(II)-tannin coordination complex, a precursor of the iron gall ink, transforms into interface-active Fe(III)-tannin species, by oxygen molecules, which form a self-assembled layer at the fluidic interface spontaneously but still controllably. Kinetic studies show that the oxidation rate is directed by the counteranion of Fe(II) precursor salts, and FeCl₂ is found to be more effective than FeSO₄ -an ingredient of iron gall ink-in the interfacial-film fabrication. The optimized protocol leads to the formation of micrometer-thick, free-standing films at the air-water interface by continuously generating Fe(III)-tannic acid complexes in situ. The durable films formed are transferable, self-healable, pliable, and postfunctionalizable, and are hardened further by transfer to the basic buffer. This O₂ -instructed film formation can be applied to other fluidic interfaces that have high O₂ level, demonstrated by emulsion stabilization and concurrent capsule formation at the oil-water interface with no aid of surfactants. The system, inspired by the iron gall ink, provides new vistas on interface engineering and related materials science.