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Issue 33, 2014
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Binding of amphiphilic and triphilic block copolymers to lipid model membranes: the role of perfluorinated moieties

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Abstract

A novel class of symmetric amphi- and triphilic (hydrophilic, lipophilic, fluorophilic) block copolymers has been investigated with respect to their interactions with lipid membranes. The amphiphilic triblock copolymer has the structure PGMA20-PPO34-PGMA20 (GP) and it becomes triphilic after attaching perfluoroalkyl moieties (F9) to either end which leads to F9-PGMA20-PPO34-PGMA20-F9 (F-GP). The hydrophobic poly(propylene oxide) (PPO) block is sufficiently long to span a lipid bilayer. The poly(glycerol monomethacrylate) (PGMA) blocks have a high propensity for hydrogen bonding. The hydrophobic and lipophobic perfluoroalkyl moieties have the tendency to phase segregate in aqueous as well as in hydrocarbon environments. We performed differential scanning calorimetry (DSC) measurements on polymer bound lipid vesicles under systematic variation of the bilayer thickness, the nature of the lipid headgroup, and the polymer concentration. The vesicles were composed of phosphatidylcholines (DMPC, DPPC, DAPC, DSPC) or phosphatidylethanolamines (DMPE, DPPE, POPE). We showed that GP as well as F-GP binding have membrane stabilizing and destabilizing components. PPO and F9 blocks insert into the hydrophobic part of the membrane concomitantly with PGMA block adsorption to the lipid headgroup layer. The F9 chains act as additional membrane anchors. The insertion of the PPO blocks of both GP and F-GP could be proven by 2D-NOESY NMR spectroscopy. By fluorescence microscopy we show that F-GP binding increases the porosity of POPC giant unilamellar vesicles (GUVs), allowing the influx of water soluble dyes as well as the translocation of the complete triphilic polymer and its accumulation at the GUV surface. These results open a new route for the rational design of membrane systems with specific properties.

Graphical abstract: Binding of amphiphilic and triphilic block copolymers to lipid model membranes: the role of perfluorinated moieties

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Publication details

The article was received on 16 Apr 2014, accepted on 03 Jun 2014 and first published on 04 Jun 2014


Article type: Paper
DOI: 10.1039/C4SM00830H
Citation: Soft Matter, 2014,10, 6147-6160
  • Open access: Creative Commons BY license
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    Binding of amphiphilic and triphilic block copolymers to lipid model membranes: the role of perfluorinated moieties

    C. Schwieger, A. Achilles, S. Scholz, J. Rüger, K. Bacia, K. Saalwaechter, J. Kressler and A. Blume, Soft Matter, 2014, 10, 6147
    DOI: 10.1039/C4SM00830H

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