Synthetic ion transporters: pore formation in bilayers via coupled activity of non-spanning cobalt-cage amphiphiles.

Three amphiphilic cobalt-cage congeners bearing a diaza-crown bridge and varying alkyl chains (1:2:3; n = 12, 16, 18) have been assessed for their ion transport across planar lipid bilayer membranes. In symmetrical electrolyte solutions, a range of ion transport activity is provoked: 1 disrupts painted (fluid) bilayers in a detergent-like mode of action; 2 forms conducting "pores" in folded (rigid) membranes with long open lifetimes (>2 min) while 3 requires the larger auxiliary solvent volume and lower lateral stress of painted membranes to effect ion transport via long-lived pores. Hill analysis of the conductance variation with monomer concentration yields coefficients (2:3; n = 2.3, 1.9) in support of dimeric (n = 2) membrane-active structures, for which the derived "pore" radii are correlated with charge-density of the transported cations and their affinity for the crown moiety. A toroidal-pore model is invoked to account for the flux of guest ions through planar bilayer membranes without a fast-diffusing intermediary or direct membrane-spanning structure.