The origin of cooperative solubilisation by hydrotropes
Literature Information
Seishi Shimizu
The signature of hydrotropic solubilisation is the sigmoidal solubility curve; when plotted against hydrotrope concentration, solubility increases suddenly after the minimum hydrotrope concentration (MHC), and reaches a plateau at higher hydrotrope concentrations. This sigmoidal curve is characteristic of cooperative phenomena, yet the true molecular basis of hydrotropic cooperativity has long remained unclear. Here we develop a theory, derived from the first principles of statistical thermodynamics using partially-open ensembles, to identify the origin of hydrophobic cooperativity. Our theory bears a close resemblance to the cooperative binding model used for protein–ligand binding. The cause of cooperativity is the enhancement of the hydrotrope m-body interaction induced by the presence of the solute; m can be estimated from the experimental solubility data.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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