Polymerization in polymerizable vesicle bilayer membranes

Polymerization reactions in lyotropic liquid crystalline phases have opened the way to the development of many novel materials. Inter alia, the two-di mensional self-assembly of amphiphiles in vesicle bilayers has attracted co nsiderable interest as an ordered reaction medium. In this study we follow three different routes to polymerize within vesicle bilayer membranes with a view to preparing novel vesicle-polymer colloids. First, we study the ves icle formation and the polymerization of functional amphiphiles carrying on e or two styryl groups. A combination of characterization techniques gives insights into bilayer properties, polymerization kinetics, and vesicle morp hology of these (polymerized) vesicles. On the basis of this reference syst em, we explore the copolymerization of monomers inserted in the matrix of p olymerizable amphiphiles. On the basis of kinetic and morphological data we prove that the copolymerization is viable if the polymerizable moieties ar e adequately chosen with respect to reactivity and location within the amph iphile matrix. Extremely deformed, albeit stable, vesicles are induced by c ross-linking inserted monomers with monofunctional amphiphiles. Tn a last s tep, we attempt the synthesis of two-dimensional interpenetrating networks employing the previously polymerized amphiphile networks as templates. The cross-linking of divinylbenzene within cross-linked membranes affords pecul iar orange-skin-like bilayer morphologies and gives evidence of the feasibi lity of the concept. Throughout the study, cryogenic electron microscopy ap pears as an indispensable means to unravel the morphology of the obtained v esicle-polymer architectures.