Solution-State Hydrostatic Pressure Chemistry: Application to Molecular, Supramolecular, Polymer, and Biological Systems.

Pressure ( P ), as one of the most inherent state quantities, has become an academic subject of study and has attracted attention for a long time for the minute control of reaction equilibria and rates, not only in the gas phase, based on the gas state equation, but also in the solution state. In the latter case, the pressure applied to the solutions is classified as hydrostatic pressure, which is a type of isotropic mechanical force. For instance, deep-sea organisms are exposed to hydrostatic pressure environments of up to 100 MPa, implying that hydrostatic pressurization plays a role in homeostatic functions at physiological levels. The pressure control of such complicated biological behavior can be addressed by thermodynamics or kinetics. In fact, the spontaneity (Δ G ) of a reaction that is governed by weak interactions (approximately 10 kcal/mol), such as electrostatic, van der Waals, hydrophobic, hydrogen bonding, and π-π stacking, is determined by the exquisite balance of enthalpy (Δ H ) and entropy changes (Δ S ), in accordance with the fundamental thermodynamic equation Δ G = Δ H - T Δ S . The mutually correlated Δ H -Δ S relationship is known as the enthalpy-entropy compensation law, in which a more negative enthalpic change (more exothermic) causes further entropic loss based on a more negative entropy change. Namely, changing the temperature ( T ) as the state quantity, except for P , is highly likely to be equal to controlling the entropy term. The solution-state entropy term is relatively vague, mainly based on solvation, and thus unpredictable, even using high-cost quantum mechanical calculations because of the vast number of solvation molecules. Hence, such entropy control is not always feasible and must be demonstrated on a trial-and-error basis. Furthermore, the above-mentioned equation can be rearranged as Δ G = Δ F + P Δ V , enabling us to control solution-state reactions by simply changing P as hydrostatic pressure based on the volume change (Δ V ). The volume term is strongly relevant to conformational changes, solvation changes, and molecular recognition upon complexation and thus is relatively predictable, that is, volumetrically compact or not, compared to the complicated entropy term. These extrathermodynamic and kinetic observations prompted us to use hydrostatic pressure as a controlling factor over a long period. Hydrostatic pressure chemistry in the solution phase has developed over the past six decades and then converged and passed the fields of mechanochemistry and mechanobiology, which are new but challenging and current hot topics in multidisciplinary science. In this Account, we fully summarize our achievements in solution-state hydrostatic pressure chemistry for smart/functional molecular, supramolecular, polymer, and biological systems. We hope that the phenomena, mechanistic outcomes, and methodologies that we introduced herein for hydrostatic-pressure-controlling dynamics can provide guidance for both theoretical and experimental chemists working in supramolecular and (bio)macromolecular chemistry, mechanoscience, materials science, and technology.