Structure of Dense Adsorption Layers of Escin at the Air-Water Interface Studied by Molecular Dynamics Simulations

Saponins are natural surfactants with high surface activity and unique surface properties. Escin is a triterpenoid saponin which has unusually high surface viscoelasticity [Golemanov et al. Soft Matter 2013, 9, 5738] and low permittivity to molecular gas diffusion of its adsorption layers. In our previous study [Tsibranska et al. Langmuir 2017, 33, 8330], we investigated the molecular origin of this unconventional behavior and found that escin molecules rapidly assemble in a compact and stable surface cluster. This behavior was explained with long-range attraction between the hydrophobic aglycones combined with intermediate dipole-dipole attraction and strong short-range hydrogen bonds between the sugar residues in the adsorbed escin molecules. In this study, we performed atomistic molecular simulations of escin molecules in dense adsorption layers with two different areas per molecule. The results show that the surfactant molecules in these systems are much less submerged in water and adopt a more upright position compared to the dilute layers studied previously. A significant number of trapped water molecules are located around the hydrophilic groups placed above the water equimolecular surface to solvate them in the dense layer. To maintain the preferred orientation of the escin molecules with respect to the interface, the most compact adsorption layer acquires a significant spontaneous curvature. The substantial elasticity of the neutral escin layers, as in our previous study, is explained with the presence of a specific interaction, which is intermediate between hydrogen bonding and dipole-dipole attraction (populated lengths in the range 0.16 to >0.35 nm), supplemented by substantial flexibility of the surfactant heads, optimal curvature of the interface, and significant normal displacement of the molecules to allow their tight surface packing. The simulations reveal long-range order within the layers, which signifies the role of the collective behavior of the saponin molecules in such dense adsorption layers.