| Abstract
| - Polymerization reactions in lyotropic liquid crystalline phases have opened the way to the developmentof many novel materials. Inter alia, the two-dimensional self-assembly of amphiphiles in vesicle bilayershas attracted considerable interest as an ordered reaction medium. In this study we follow three differentroutes to polymerize within vesicle bilayer membranes with a view to preparing novel vesicle−polymercolloids. First, we study the vesicle formation and the polymerization of functional amphiphiles carryingone or two styryl groups. A combination of characterization techniques gives insights into bilayer properties,polymerization kinetics, and vesicle morphology of these (polymerized) vesicles. On the basis of this referencesystem, we explore the copolymerization of monomers inserted in the matrix of polymerizable amphiphiles.On the basis of kinetic and morphological data we prove that the copolymerization is viable if thepolymerizable moieties are adequately chosen with respect to reactivity and location within the amphiphilematrix. Extremely deformed, albeit stable, vesicles are induced by cross-linking inserted monomers withmonofunctional amphiphiles. In a last step, we attempt the synthesis of two-dimensional interpenetratingnetworks employing the previously polymerized amphiphile networks as templates. The cross-linking ofdivinylbenzene within cross-linked membranes affords peculiar orange-skin-like bilayer morphologiesand gives evidence of the feasibility of the concept. Throughout the study, cryogenic electron microscopyappears as an indispensable means to unravel the morphology of the obtained vesicle−polymer architectures.
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