Solvation properties of natural and synthetic ionophores. I. Stoichiometry of complexes with alkali and alkaline earth cations in aprotic organic solvents.

Ion-solvent interactions play a very important role in the studies of stoichiometry, structure, and stability of complexes of cations with natural and synthetic ionophores. These compounds are extremely useful in study of the interaction of neutral salts with macromolecules and the mechanism of cation transport across biological membranes. Knowledge of the ionophore solvation properties enables one to choose a suitable solvent for complexation studies and to obtain detailed information on the solvent effect. We would like to present in this paper a very simple method of estimating the solvation properties of ionophores. We treat the ligand as an assembly of individual noninteracting binding sites. The solvation properties of solvents can be used to represent the solvation sites in natural and synthetic ligands. The solvation properties are represented by the Gutmann donor number (DN) of the model solvent. We can define the solvation ability of a ligand binding site be "donor number of binding site" (DN binding site), which in turn can be represented by the DN of the appropriate model solvent. The average DN of the ligand (DN average) is defined as [xi ni-1 (DN binding site)i]/n, where n is the number of the ligand binding sites. Comparison of the DN average with the DN solvent, together with the knowledge of the composition of the system, characterizes remarkably well the solvation properties of the ligand. This model explains (a) the stoichiometry of many alkali and alkaline earth cation complexes with natural and synthetic ligands in aprotic organic solvents, (b) the transport of alkali and alkaline earth cations across lipid bilayers, and (c) how polypeptides and proteins interact with neutral salts in solutions.