Cross-Linking Polymerizations in Two-Dimensional Assemblies

Abstract

Polymerization of monomeric lipids in an assembly proceeds in a linear or cross-linking manner depending on the number of polymerizable groups per monomeric lipid. Lipids that contain a single reactive moiety in either of the hydrophobic tails or associated with the hydrophillic head group yield linear polymers. Polymerization of lipids with reactive groups in each hydrophobic tail generally yield cross-linked polymeric networks. This report describes three approaches to the characterization of the gel point for polymerizations constrained by the two-dimensional nature of lipid bilayers. The gel point for two-dimensional lipid assemblies was determined by correlation of the onset of significant changes in the physical properties of the polymerized bilayers with the bilayer composition. The properties examined in this study were the lateral diffusion of a small molecule probe of the bilayer, the stability of polymerized bilayer vesicles in the presence of surfactants, and the solubility of lipid polymers isolated from the bilayers after removal of water. Each of the three methods used indicated that a substantial mole fraction (0.25−0.35) of the bis-substituted lipid was necessary to cause cross-linking of the bilayer. The general agreement between the methods provides confidence that these results accurately indicate the relative inefficiency of the cross-linking process in bilayers composed of lipids having a reactive group at the hydrophobic terminus of the lipid tail(s). The possible explanations for the inefficient nature of the lipid bilayer cross-linking are discussed with regard to the preferred conformation of monomeric lipids in the bilayer, the motions of the lipid tails, and competing side reactions. These studies provide a new insight into the behavior of polymerizations in organized assemblies, which will aid in the design of new materials based on bilayers or other types of assemblies, e.g. inverted hexagonal or bicontinuous cubic phases.

Ultra-High Vacuum Surface Analysis Study of Rhodopsin Incorporation into Supported Lipid Bilayers

“…Although cross-linked PSLBs are formed by both methods, previous studies on poly(bis-SorbPC) vesicles have shown that redox initiation produces a greater degree of polymerization (X n = 50-500) than UV irradiation (X n = 3-10). [32][33][34] A similar trend likely occurs in bis-SorbPC PSLBs polymerized by these two methods, and significant differences in their respective structural properties have been observed. 14,15 The origin of these differences may be different propagation mechanisms for the two methods.…”

Supramolecular Materials via Polymerization of Mesophases of Hydrated Amphiphiles

“…38 The onset of cross-linking was determined by changes in lipid lateral diffusion, bilayer vesicle stability, and polymer solubility. These data indicated that a substantial mole fraction (0.30 ± 0.05) of the bis-SorbPC, as in the case of AcrylPC (see section II.A), was necessary for bilayer crosslinking.…”

Photopolymerization of Diacetylene Lipid Bilayers and Its Application to the Construction of Micropatterned Biomimetic Membranes

“…Upon polymerization, the bilayers became significantly less soluble in organic solvents or detergent solutions. [17][18][19][20] In addition, decrease in the lateral diffusion constant and the permeation coefficient of the bilayers was observed. 21,22 Micropatterning of SPBs by lithographic photopolymerization of lipid bilayers aims to achieve both spatial control and stabilization of biomimetic membranes.…”