Collective Solvation and Transport at Tetrahydrofuran-Silica Interfaces for Separation of Aromatic Compounds: Insight from Molecular Dynamics Simulations.

We have performed umbrella sampling molecular dynamics simulations to study the separation mechanism of aromatic compounds at the tetrahydrofuran (THF)-methanol-silica interface by liquid chromatography. Solute molecules with different polarities (naphthol and naphthalene) are selected as representative aromatic compounds. For the polar solute (naphthol), the free energy profile shows a deep minimum near the THF-silica interface, suggesting strong interactions with the polar surface. When methanol is added to the interface, there is a sharp increase in naphthol's free energy minimum, and the corresponding diffusion dynamics also undergoes a dramatic change. These findings explain the fast separation mechanism in recent experiments of separating fused ring compounds in asphaltenes with liquid chromatography. Further solvation structure and orientation analysis suggest that apolar and polar solutes may find their own comfort zones several angstroms away from the interface, and their phenyl ring's orientations would undergo a parallel-to-perpendicular transition as the solute molecule moves away from the surface. Extending our simulation studies to systems with different solute concentrations reveals that there is a decrease in the adsorption free energy accompanied by enhanced surface diffusion as the solute concentration increases, which is related to the crowding in the interfacial layers. Our simulation analysis gives a detailed microscopic description of solute solvation and transport at the THF-silica chromatography interface and will be helpful for improving separation protocols in future applications.