Multicomponent Self-Assembly\nand Self-Sorting of Polymer\nMicelles in Water: Selective and Switchable Association by Kinetic\nor Thermodynamic Control

Herein, we report multicomponent self-assembly and self-sorting\nof polymer micelles in water using mixtures of an anionic random copolymer\nbearing sodium sulfonate and dodecyl groups and random copolymers\ncarrying poly(ethylene glycol) (PEG) and alkyl groups. In pure water,\nthe anionic copolymer is co-self-assembled with the PEG copolymers\nto form anion/PEG-fused micelles with a controlled aggregation number.\nBy designing the composition or alkyl groups of PEG copolymers, the\nfused micelle is reversibly self-sorted into discrete anion or PEG\nmicelles in the presence of NaCl. Co-self-assembly of the anionic\ncopolymer and PEG copolymers is kinetically or thermodynamically controlled,\ndepending on the dynamic properties of the PEG copolymer micelles.\nThus, the selective self-assembly of ternary copolymers is also controllable\nand switchable by temperature: A kinetically favored anion/PEG-fused\nmicelle is predominantly formed in the presence of a kinetically frozen\nPEG micelle at low temperature, whereas the fused micelle is transformed\nvia polymer chain exchange upon heating into a thermodynamically more\nstable anion/PEG-fused micelle.