title: Binding of amphiphilic and triphilic block copolymers to lipid model membranes: the role of perfluorinated moieties.
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 PGMA(20)-PPO(34)-PGMA(20) (GP) and it becomes triphilic after attaching perfluoroalkyl moieties (F9) to either end which leads to F(9)-PGMA(20)-PPO(34)-PGMA(20)-F(9) (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.
authors.affiliation: Institute of Chemistry, Martin Luther University Halle-Wittenberg, 06120 Halle (Saale), Germany. christian.schwieger@chemie.uni-halle.de.
authors.forename: Christian
authors.initials: C
authors.lastname: Schwieger
authors.forename: Anja
authors.initials: A
authors.lastname: Achilles
authors.forename: Sven
authors.initials: S
authors.lastname: Scholz
authors.forename: Jan
authors.initials: J
authors.lastname: Rüger
authors.forename: Kirsten
authors.initials: K
authors.lastname: Bacia
authors.forename: Kay
authors.initials: K
authors.lastname: Saalwaechter
authors.forename: Jörg
authors.initials: J
authors.lastname: Kressler
authors.forename: Alfred
authors.initials: A
authors.lastname: Blume
mesh_terms: D000179:Acrylates / Q000737:chemistry; D000327:Adsorption; D002152:Calorimetry, Differential Scanning; D002851:Chromatography, High Pressure Liquid; D006838:Hydrocarbons / Q000737:chemistry; D006860:Hydrogen Bonding; D057927:Hydrophobic and Hydrophilic Interactions; D008051:Lipid Bilayers / Q000737:chemistry*; D008055:Lipids / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D018613:Microscopy, Confocal; D011108:Polymers / Q000737:chemistry*; D011109:Polymethacrylic Acids / Q000737:chemistry*; D011409:Propylene Glycols / Q000737:chemistry*; D012235:Rhodamines / Q000737:chemistry; D013696:Temperature; D013816:Thermodynamics
chemical_list: D000179:Acrylates; D006838:Hydrocarbons; D008051:Lipid Bilayers; D008055:Lipids; D011108:Polymers; D011109:Polymethacrylic Acids; D011409:Propylene Glycols; D012235:Rhodamines; C012504:polypropylene glycol