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Solution-State Hydrostatic Pressure Chemistry: Application to Molecular, Supramolecular, Polymer, and Biological
Hiroaki Mizuno1, Gaku Fukuhara1,2
1Department of Chemistry, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
Accounts of Chemical Research
|June 3, 2022
Summary
Hydrostatic pressure offers a predictable way to control chemical reactions in solutions by influencing volume changes, unlike complex entropy-based temperature control. This approach is vital for understanding and manipulating molecular, supramolecular, polymer, and biological systems.
Area of Science:
- Solution-state chemistry
- Mechanochemistry
- Mechanobiology
- Thermodynamics and kinetics
Background:
- Pressure is a fundamental state quantity influencing reaction equilibria and rates in both gas and solution phases.
- Hydrostatic pressure, an isotropic mechanical force, is crucial in biological systems (e.g., deep-sea organisms) and can be controlled via thermodynamics or kinetics.
- Controlling reactions via enthalpy-entropy compensation is complex due to the unpredictable nature of solution-state entropy, which is heavily influenced by solvation.
Purpose of the Study:
- To explore the use of hydrostatic pressure as a controllable factor in solution-state chemistry.
- To summarize achievements in applying hydrostatic pressure to smart/functional molecular, supramolecular, polymer, and biological systems.
- To provide guidance for chemists in supramolecular, (bio)macromolecular chemistry, mechanoscience, and materials science.
Main Methods:
- Utilizing the thermodynamic equation rearranged as ΔG = ΔF + PΔV, where hydrostatic pressure (P) is manipulated.
- Leveraging the predictability of volume changes (ΔV) associated with conformational, solvation, and molecular recognition events.
- Investigating hydrostatic pressure's influence on reaction dynamics and equilibria in various chemical systems.
Main Results:
- Hydrostatic pressure provides a more predictable means of controlling reactions compared to temperature-induced entropy changes.
- Volume changes (ΔV) are key determinants in pressure-controlled reactions, relating to molecular packing, solvation, and complexation.
- Hydrostatic pressure chemistry has evolved over six decades, converging with mechanochemistry and mechanobiology.
Conclusions:
- Hydrostatic pressure is a powerful tool for controlling solution-state reactions due to its predictable impact on volume.
- This approach offers a viable alternative to entropy-based control, particularly for complex biological and materials systems.
- The methodologies and findings presented can guide future research in pressure-controlled molecular and materials science.
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