Kinetically Controlled Preparation of Worm-like Micelles with Tunable Diameter/Length and Structural Stability.

Anisotropic nanoparticles such as worm-like micelles have aroused much attention due to their promising applications from templates to drug delivery. The fabrication of worm-like micelles with tunable structural stability and control over their diameter and length is of great importance but still challenging. Herein, we report a kinetically controlled ring-opening metathesis polymerization-induced self-assembly (ROMPISA) for the robust preparation of kinetically trapped worm-like micelles with tunable diameter/length at enlarged experimental windows by the rational manipulation of kinetic factors, including solvent property, temperature, and π-π stacking effects. The resultant worm structures were thermodynamically metastable and capable of excellent structural stability at room temperature due to the kinetic trapping effect. At elevated temperatures, these thermodynamically metastable worms could undergo morphology evolution into vesicular structures in a controlled manner. Moreover, the structural stability of worms could also be significantly enhanced by in situ cross-linking. Overall, this kinetically controlled ROMPISA opens a new avenue for PISA chemistry that is expected to prepare "smart" polymer materials by manipulating kinetic factors.