Chemical control of colloidal self-assembly driven by the electrosolvation force

Self-assembly of matter in solution generally relies on attractive interactions that overcome entropy and drive the formation of higher-order molecular and particulate structures. Such interactions are central to a variety of molecular processes, e.g., crystallisation, biomolecular folding and condensation, pathological protein aggregation and biofouling. The electrosolvation force introduces a distinct conceptual paradigm to the existing palette of interactions that govern the spontaneous accretion and organisation of matter. However, an understanding of the underlying physical chemistry, and therefore the ability to exert control over and tune the interaction, remains incomplete. Here we provide further evidence that this force arises from the structure of the interfacial electrolyte. Neutral molecules such as a different solvent, osmolytes or surfactants, may - even at very low concentrations in the medium - disrupt or reinforce pre-existing interfacial solvent structure, thereby delivering unanticipated chemical tuning of the ability of matter to self-assemble. The observations present unexpected mechanistic elements that may explain the impact of co-solvents and osmolytes on protein structure, stability and biomolecular condensation. Our findings thus furnish insight into the microscopic mechanisms that drive the emergence of order and structure from molecular to macroscopic scales in the solution phase.