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Dynamic Control over Aqueous Poly(butadiene-b-ethylene oxide) Self-Assembly through Olefin Metathesis

We show that olefin metathesis can be used in an extremely simple process to rapidly alter the morphology of self-assembled poly(butadiene-b-ethylene oxide) (PB–PEO) dispersions in situ. The addition of a water-insoluble Hoveyda–Grubbs catalyst to aqueous assemblies of PB–PEO leads to degradation of the hydrophobic PB block by well-established metathesis pathways and a concomitant change in the composition of the block copolymer. This phenomenon drives morphological transitions characterized by rapidly decreasing sizes of the self-assembled aggregates, the ultimate extent of which is readily controlled by catalyst concentration. Exemplary cases are presented in which transitions from worm-like micelles to spherical micelles or from vesicles to worm-like micelles can be accomplished within minutes.