Assembly of Dumbbell- and Bola-Shaped Amphiphiles: Vesicles with Condensed Hydrophobic Domains or Blackberry-type Structures with Porous Surfaces?

Dumbbell- and bola-shaped amphiphiles are commonly expected to self-assemble into vesicles with condensed hydrophobic domains due to the dominant hydrophobic interaction. In this work, we examined the assemblies of the dumbbell-shaped AC60-AC60amphiphile, with two carboxylic acid-functionalized fullerenes (AC60) polar head groups linked by an organic tether, and found that they assemble into hollow, spherical blackberry-type structures with porous surfaces, judged by their smaller assemblies in organic solvents with higher polarity and in aqueous solutions with high pH. We attribute the formation of blackberry structures to the organic tether that may be too short to fill up a condensed hydrophobic domain, as confirmed by all-atom simulations. This is further proved by noticing that several bola-type macromolecules with hydrophilic polyethylene glycol (PEG) chain being the linker and no hydrophobic components, AC60-PEG-AC60, can also self-assemble into hollow, spherical assemblies and demonstrate similar pH response as the assemblies from AC60-AC60dumbbells. Therefore, we conclude that the driving force of the self-assembly for these dumbbell- or bola-shaped molecules is counterion-mediated attraction from the two AC60head groups rather than the hydrophobic interaction due to the organic linkers. The so-formed blackberry structures here, as well-studied before in other systems, possess porous surfaces, making these charged amphiphiles a valuable model for designing stable nanocontainers with controllable porosity to the change of the environment.