Strong reversible Fe3+-mediated bridging between dopa-containing protein films in water

Metal-containing polymer networks are widespread in biology, particularly for load-bearing exoskeletal biomaterials. Mytilus byssal cuticle is an especially interesting case containing moderate levels of Fe(3+) and cuticle protein-mussel foot protein-1 (mfp-1), which has a peculiar combination of high hardness and high extensibility. Mfp-1, containing 13 mol % of dopa (3, 4-dihydroxyphenylalanine) side-chains, is highly positively charged polyelectrolyte (pI approximately 10) and didn't show any cohesive tendencies in previous surface forces apparatus (SFA) studies. Here, we show that Fe(3+) ions can mediate unusually strong interactions between the positively charged proteins. Using an SFA, Fe(3+) was observed to impart robust bridging (W(ad) approximately 4.3 mJ/m(2)) between two noninteracting mfp-1 films in aqueous buffer approaching the ionic strength of seawater. The Fe(3+) bridging between the mfp-1-coated surfaces is fully reversible in water, increasing with contact time and iron concentration up to 10 microM; at 100 microM, Fe(3+) bridging adhesion is abolished. Bridging is apparently due to the formation of multivalent dopa-iron complexes. Similar Fe-mediated bridging (W(ad) approximately 5.7 mJ/m(2)) by a smaller recombinant dopa-containing analogue indicates that bridging is largely independent of molecular weight and posttranslational modifications other than dopa. The results suggest that dopa-metal interactions may provide an energetic new paradigm for engineering strong, self-healing interactions between polymers under water.