Can Polarity-Inverted Surfactants Self-Assemble in Nonpolar Solvents?

We investigate the self-assembly process of a surfactant with inverted polarity in water and cyclohexane using both all-atom and coarse grained hybrid particle-field molecular
dynamics simulations. Unlike conventional surfactants, the molecule under study proposed in a recent experiment (M. Facchin et al., RSC Adv. 2017, 7, 15337–15341) is
formed by a rigid and compact hydrophobic adamantane moiety, and a long and floppy triethylene glycol tail. In water, we report the formation of stable inverted micelles with the adamantane heads grouping together into a hydrophobic core, and the tails forming hydrogen bonds with water. By contrast, multi-microsecond simulations do not provide evidence of stable micelle formation in cyclohexane. Validating the computational results by comparison with experimental diffusion constant and small-angle neutron scattering intensity, we show that at laboratory thermodynamic conditions the mixture resides in the supercritical region of the phase diagram, where aggregated and free surfactant states co-exist in solution. Our simulations also provide indications about how to escape this region, to produce thermodynamically stable micellar forms.