Dissolution Parameters Reveal Role of Structure and Solvent in Molecular Gelation

The relationship between thermodynamic dissolution parameters (enthalpy and entropy) and gelation ability was examined for two different classes of compounds in three different solvent systems. In total, 11 dip eptides and 19 pyridines were synthesized and screened for gelation in aqueous and organic solvents, respectively. The dissolution parameters were determined from the variable-temperature solubilities using the van't Hoff equation. These studies revealed that the majority of gelators had higher dissolution enthalpies and entropies compared to nongelators, consistent with the notion that gelators have stronger intermolecular interactions and more order in the solid state. The dissolution parameters were also found to be solvent-dependent, suggesting that solvent solute interactions are also important in gelation. Overall, these results indicate that converting nongelators into gelators is attainable when structural modifications or a change in solvent lead to increases in the dissolution parameters.