The empirical force field method is used to calculate conformations and energies of the natural ion carrier enniatin B (EnB) and its alkali ion complexes. Solvent effects are circumvented by focusing the study on conformational characteristics and trends in ionophoric behavior, which do not require an evaluation of solvent interactions. A few calculated, low-energy conformations of the EnB ring are presented. The C3-symmetric conformation of EnB is analyzed in detail. Its rotational isomeric states of the isopropyl side chains are found to interact strongly with its carbonyl and N-methyl groups, thus restricting significantly the flexibility of EnB's skeletal ring. Two kinds of 1 : 1 EnB-ion complexes are obtained: internal and external. In internal complexes, the ion is located at or near the center of an octahedral cavity formed by the six carbonyls of EnB and binds to all these carbonyls. The large strain energy imposed on the ligand by bending the carbonyls inward destabilizes the internal binding. E n n i a t i n s are natural ion carriers whose biological functions are determined by their ability to transport cations across lipid bilayer membranes. Enniatins, and particularly enniatin B,' Abbreviations: EnB, enniatin B; (LacAla)3, EnB methyl side chain analogue [ (-~-lactyl-~-N-methylalanyl)~]; Lac6, EnB hexalactyl analogue [ (-D-laCtyl-L-laCtyl)3].