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What could be the self-assembly behavior in aqueous solution for an amphiphilic block copolymer with a very flexible hydrophobic backbone possessing however a liquid crystalline (LC) order? To answer this question, five amphiphilic block copolymers were prepared by grafting, via a thiol−ene addition reaction, four different thiol-functionalized LC mesogens or LC-like side groups on two commercially available poly(ethylene oxide)- block -poly(butadiene) (PEO- b -PB) polymers. These copolymers form monodisperse nanospheres in dilute deionized water with the aid of 1,4-dioxane as cosolvent (dioxane−H 2 O system), while in the THF−H 2 O system, some give heterogeneous polydisperse micelles and others form large hollow concentric spherical vesicles (“Russian dolls” arrangement). Smectic stripes inside the vesicles and the nanospheres are clearly visualized by cryo-TEM technique.
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Yang et al. (2010) studied this question.
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