Flower-Like Multicompartment Micelles with Janus-Core Self-Assembled from Fluorocarbon-Terminated Pluronics

Multicompartment micelles (MCMs), whose cores have at least two compartments, show potential applications in various areas, but the synthesis of polymers for preparing MCMs is usually tedious and time-consuming. In this work, two well-defined telechelic fluorocarbon-terminated triblock copolymers, F 8 -PEO 100 -PPO 65 -PEO 100 -F 8 (F 8 -F127-F 8 ) and F 8 -PEO 132 -PPO 50 -PEO 132 -F 8 (F 8 -F108-F 8 ), are synthesized via a single-step coupling reaction of Pluronics F127 or F108 with perfluoro-1-octanesulfonyl fluoride and characterized by Fourier-transform infrared and NMR spectroscopies, as well as gel permeation chromatography and surface tensiometry. Both of these fluorocarbon-terminated Pluronics can self-assemble into spherical MCMs with Janus-core in aqueous solution, as evidenced by transmission electron microscopy imaging. Since the lipophilic block (PPO) and fluorophilic segments (F 8 ) are separated by the hydrophilic blocks (PEO), these fluorocarbon-terminated Pluronics will loop to give rise to flower-like MCMs, and the calculations based on thermodynamics and dynamics support the formation of such unique aggregates. A “pre-self-assembly” mechanism is proposed to explain the formation process of flower-like MCMs with Janus-core prepared by these telechelic fluorocarbon-terminated triblock copolymers.