Shear Induced Morphological Transformation of Large Compound Micelles Formed by Glutathione End-capped Poly(4-vinylpyridine)

Here we report novel shear-sensitive polymeric large compound micelles (LCMs) formed by self-assembly of glutathione end-capped poly(4-vinylpyridine) (GP4VP) in water containing 4 vol% methanol. The amphiphile prefers to form the kinetically stabilized LCMs due to the small length ratio of the hydrophilic part to the hydrophobic part; the encapsulation of the hydrophilic part within LCMs causes only a small enthalpy loss from a thermodynamic view. Sheared by vortex flows generated by vigorous stir, the LCMs evolve to thick wall vesicles, thin wall vesicles, broken vesicles and "pearl-necklace" structures consecutively. The high flexibility of the LCMs and the internal tension caused by the encapsulation of the hydrophilic part are responsible for the high shear sensitivity of the LCMs.