Thermodynamics of Protein-Ligand Association and Hydration

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Prediction and interpretation of the hydration entropies of monovalent cations and anions

International audienceThe hydration entropy of the monovalent cations and anions are calculated directly from molecular dynamics simulations of the hydrated ion and bulk water using theory previously applied to the hydration of noble gases [Irudayam and Henchman, J. Phys.: Cond. Matter, 2010, 22, 284108]. Extensions are included to account for differential hydrogen-bonding of first-shell waters with themselves, the ion, and bulk water. The entropies, enthalpies and Gibbs energies agree reasonably with simulation and experiment when the effect of force field is taken into account. The anions' entropy losses are mostly vibrational and librational, consistent with their stronger hydration. The cations' entropy losses are mostly orientational which implies fewer hydrogen-bond arrangements because the cation substantially inhibits the ability of surrounding water molecules to accept hydrogen bonds. Owing to the many entropy terms and different decompositions, it is shown that the terms of kosmotropes and chaotropes must be appropriately applied so as not to lead to contradictions. It is also proposed that the number of hydrogen bond arrangements help explain the ordering in Hofmeister series of ions whereby anions increase this number but cations decrease it