Interfacial Rheology of Lanthanide Binding Peptide Surfactants at the Air-Water Interface

Peptide surfactants (PEPS) are studied to capture and retain rare earth elements (REEs) at air-water interfaces to enable REE separations. Peptide sequences, designed to selectively bind REEs, depend crucially on the position of ligands within their binding loop domain. These ligands form a coordination sphere that wraps and retains the cation. We study variants of lanthanide binding tags (LBTs) designed to complex strongly with Tb^3+. The peptide LBT^5- (with net charge -5) is known to bind Tb^3+ and adsorb with more REE cations than peptide molecules, suggesting that undesired non-specific Coulombic interactions occur. Rheological characterization of interfaces of LBT^5- and Tb^3+ solutions reveal the formation of an interfacial gel. To probe whether this gelation reflects chelation among intact adsorbed LBT^5-:Tb^3+ complexes or destruction of the binding loop, we study a variant, LBT^3-, designed to form net neutral LBT^3-:Tb^3+ complexes. Solutions of LBT^3- and Tb^3+ form purely viscous layers in the presence of excess Tb^3+, indicating that each peptide binds a single REE in an intact coordination sphere. We introduce the variant RR-LBT^3- with net charge -3 and anionic ligands outside of the coordination sphere. We find that such exposed ligands promote interfacial gelation. Thus, a nuanced requirement for interfacial selectivity of PEPS is proposed: that anionic ligands outside of the coordination sphere must be avoided to prevent the non-selective recruitment of REE cations. This view is supported by simulation, including interfacial molecular dynamics simulations, and interfacial metadynamics simulations of the free energy landscape of the binding loop conformational space.