Supramolecular “Step Polymerization” of Preassembled Micelles: A Study of “Polymerization” Kinetics

In nature, sophisticated functional materials are created through hierarchical self‐assembly of nanoscale motifs, which has inspired the fabrication of man‐made materials with complex architectures for a variety of applications. Herein, a kinetic study on the self‐assembly of spindle‐like micelles preassembled from polypeptide graft copolymers is reported. The addition of dimethylformamide and, subsequently, a selective solvent (water) can generate a “reactive point” at both ends of the spindles as a result of the existence of structural defects, which induces the “polymerization” of the spindles into nanowires. Experimental results combined with dissipative particle dynamics simulations show that the polymerization of the micellar subunits follows a step‐growth polymerization mechanism with a second‐order reaction characteristic. The assembly rate of the micelles is dependent on the subunit concentration and on the activity of the reactive points. The present work reveals a law governing the self‐assembly kinetics of micelles with structural defects and opens the door for the construction of hierarchical structures with a controllable size through supramolecular step polymerization. Preassembled micelles are found to be able to end‐to‐end “polymerize” into 1D hierarchical nanowires. Experimental results combined with dissipative particle dynamics simulations show that the polymerization kinetics follow a step‐growth polymerization mechanism with a second‐order reaction characteristic. The assembly rate of the micelles can be adjusted by the subunit concentration and the solvent condition.