Wetting of a Dynamically Patterned Surface Is a Time-Dependent Matter

In nature and many technological applications, aqueous solutions are in contact with patterned surfaces, which are dynamic over time scales spanning from ps to μs. For instance, in biology, exposed polar and apolar residues of biomolecules form a pattern, which fluctuates in time due to side chain and conformational motions. At metal/and oxide/water interfaces, the pattern is formed by surface topmost atoms, and fluctuations are due to, e.g., local surface polarization and rearrangements in the adsorbed water layer. All these dynamics have the potential to influence key processes such as wetting, energy relaxation, and biological function. Yet, their impact on the water H-bond network remains often elusive. Here, we leverage molecular dynamics to address this fundamental question at a self-assembled monolayer (SAM)/water interface, where ns dynamics is induced by frustrating SAM-water interactions via methylation of the terminal -OH groups of poly(ethylene glycol) (PEG) chains. We find that surface dynamics couples to the water H-bond network, inducing a response on the same ns time scale. This leads to time fluctuations of local wetting, oscillating from hydrophobic to hydrophilic environments. Our results suggest that rather than average properties, it is the local─ both in time and space─ solvation that determines the chemical-physical properties of dynamically patterned surfaces in water.