Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behavior. Part 2: Domain Formation by Self-Assembly in Lipid Bilayer Membranes

• Published in: Polymers Vol. 9; no. 10; p. 476
• Main Authors: Werner, Stefan, Ebenhan, Jan, Poppe, Marco, Poppe, Silvio, Ebert, Helgard, Tschierske, Carsten, Bacia, Kirsten
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 29-09-2017; MDPI
• Subjects: Chain branching; Chains; Ethylene oxide; Membranes; Self-assembly; Signaling; amphiphiles; self-assembly; phase separation; bolaamphiphiles; self-organization; membrane organization; confocal fluorescence microscopy; giant unilamellar vesicles; polyphiles; umbrella model
• ISSN: 2073-4360; 2073-4360
• DOI: 10.3390/polym9100476

Supramolecular self-assembly of membrane constituents within a phospholipid bilayer creates complex functional platforms in biological cells that operate in intracellular signaling, trafficking and membrane remodeling. Synthetic polyphilic compounds of macromolecular or small size can be incorporated into artificial phospholipid bilayers. Featuring three or four moieties of different philicities, they reach beyond ordinary amphiphilicity and open up avenues to new functions and interaction concepts. Here, we have incorporated a series of X-shaped bolapolyphiles into DPPC (1,2-dipalmitoyl-
-glycero-3-phosphocholine) bilayers of giant unilamellar vesicles. The bolapolyphiles consist of a rod-like oligo(phenylene ethynylene) (OPE) core, hydrophilic glycerol-based headgroups with or without oligo(ethylene oxide) expansions at both ends and two lateral alkyl chains attached near the center of the OPE core. In the absence of DPPC and water, the compounds showed thermotropic liquid-crystalline behavior with a transition between polyphilic and amphiphilic assembly (see part 1 in this issue). In DPPC membranes, various trends in the domain morphologies were observed upon structure variations, which entailed branched alkyl chains of various sizes, alkyl chain semiperfluorination and size expansion of the headgroups. Observed effects on domain morphology are interpreted in the context of the bulk behavior (part 1) and of a model that was previously developed based on spectroscopic and physicochemical data.