Self-Assembly of Escin Molecules at the Air–Water Interface as Studied by Molecular Dynamics

Escin belongs to a large class of natural biosurfactants, called saponins, that are present in more than 500 plant species. Saponins are applied in the pharmaceutical, cosmetics, and food and beverage industries due to their variously expressed bioactivity and surface activity. In particular, escin adsorption layers at the air–water interface exhibit an unusually high surface elastic modulus (>1100 mN/m) and a high surface viscosity (ca. 130 N·s/m). The molecular origin of these unusual surface rheological properties is still unclear. We performed classical atomistic dynamics simulations of adsorbed neutral and ionized escin molecules to clarify their orientation and interactions on the water surface. The orientation and position of the escin molecules with respect to the interface, the intermolecular interactions, and the kinetics of molecular aggregation into surface clusters are characterized in detail. Significant differences in the behavior of the neutral and the charged escin molecules are observed. The neutral escin rapidly assembles in a compact and stable surface cluster. This process is explained by the action of long-range attraction between the hydrophobic aglycones, combined with intermediate dipole–dipole attraction and short-range hydrogen bonds between the sugar residues in escin molecules. The same interactions are expected to control the viscoelastic properties of escin adsorption layers.