Self-Assembly of Polymer Tethered Molecular Nanoparticle Shape Amphiphiles in Selective Solvents

Well-defined giant molecular shape amphiphiles possessing a hydrophilic head with definite shape and size and a linear, hydrophobic polymeric tail with a length suitable to resemble the typical structure of a small-molecule surfactant were synthesized recently and were able to self-assemble into various morphologies in selective solvents. We investigated the self-assembly of shape amphiphiles consisting of a hydrophilic head and one or more hydrophobic tails using the dissipative particle dynamics (DPD) approach. The micellar morphology can transform from vesicles to worm-like cylinders and further to spheres by increasing the interaction parameter between the hydrophilic heads. The simulation results are in agreement with the experimental observations. Furthermore, the self-assembled aggregates exhibit a rich variety of morphological structures, such as spheres, vesicles, worm-like cylinders, pupa-like micelles, disk-like micelles, and segmented rod-like micelles, etc. We demonstrate how to create various morphologies through varying the interaction parameter between hydrophilic head and solvents, the length of hydrophobic tail, the size of hydrophilic head, and the number of hydrophobic tails. Most importantly, we find an interesting strategy for constructing segmented rod-like micelles through changing the size of the hydrophilic head, while using simple polymer tethered molecular nanoparticle amphiphiles as the elementary building blocks. In addition, vesicles prefer to form for more hydrophobic tails under identical conditions in solutions