Controlling the cooperativity in the supramolecular polymerization of ionic discotic amphiphiles via electrostatic screening

In a combined experimental and theoretical approach, we investigate the supramolecular polymerization of ionic discotic amphiphiles into nanorods of varying mean length, depending on the temperature and ionic strength of the buffered aqueous solution. Invoking a nucleated supramolecular polymerization model that explicitly deals with the effects of screened Coulomb interactions, we correlate the degree of cooperativity of the supramolecular polymerization with the ionic strength of the solution, as probed by means of circular dichroism spectroscopy. Experiment and theory show that electrostatic interactions between the amphiphiles in the rods make the polymerization less cooperative, implying that the larger the concentration of mobile ions in the solution the larger the cooperativity due to their screening effect. We furthermore extract quantitative information about the effective surface charge densities of the supramolecular nanorods in solution, a parameter that has been particularly difficult to determine experimentally in other related self-assembled systems.