Enthalpies of solution, limiting solubilities, and partial molar heat capacities of n-alcohols in water and in trehalose crowded media

The enthalpies of solution of alcohols were determined by calorimetry in HEPES and (HEPES + trehalose) at 298.15 K. The used methodology and experiment’s design allowed us to extract from a single titration experiment the enthalpy of solution (ΔsolHm), the limiting solubility of the alcohol in each aqueous media, and an estimation of the enthalpy of solution of water in the alcohol phase. From these values the changes in Gibbs energy (ΔsolGm) and in entropy (ΔsolSm) of solution were derived. A decrease in solubility for 1-butanol and 1-pentanol in the crowded media (HEPES + trehalose) was observed which is driven by a significant decrease in the favorable enthalpy of solution. The partial molar heat capacity, in each media was determined in our heat capacity drop calorimeter, also at 298.15 K. A significant decrease of the partial molar heat capacity was observed for both alcohols in (HEPES + trehalose), which together with the obtained decrease in favorable ΔsolHm, is consistent with a decrease in hydrophobic solvation, as a result of a decrease in free solvent availability induced by the trehalose. Finally, we tentatively predict that in the aqueous media of the crowded solutions that characterize cells and biological fluids, solutes with low aqueous solubility will be more soluble, whereas the solubility of highly polar solutes will be reduced.