Domains in cationic lipid plus polyelectrolyte bilayer membranes: detection and characterization via 2H nuclear magnetic resonance.
2H nuclear magnetic resonance (NMR) spectroscopy of choline-deuterolabeled 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC-alpha-d2 and POPC-beta-d2) has been used to detect and quantify domain formation induced in cationic lipid-containing bilayers upon the addition of anionic polyelectrolytes. Three different polyelectrolytes, poly(sodium 4-styrenesulfonate) or PSSS, poly(sodium acrylate) or PACA, and poly(sodium glutamate) or PGLU, were added to POPC lipid bilayers containing 1,2-dioleoyl-3-(dimethylamino)propane (DODAP) as the cationic amphiphile. All three polyelectrolytes produced two-component 2H NMR spectra, consistent with two populations of POPC, one polyelectrolyte-bound and another polyelectrolyte-free. The relative intensities of the two spectral components provided the relative amounts of the two POPC populations. The 2H NMR quadrupolar splitting from either spectral component provided the DODAP content of the particular POPC population. The two POPC populations differed in that the polyelectrolyte-bound population contained a stoichiometric polyelectrolyte anion:DODAP cation ratio leading to enrichment with respect to DODAP, while the polyelectrolyte-free population was depleted of DODAP. Estimates of the size of a polyelectrolyte-defined domain revealed a constant number of bound DODAP but a flexible number of bound POPC, which increased in proportion to the global POPC content. The most compact domains were formed by the most hydrophobic polyelectrolyte, PSSS, while the most expansive domains were formed by the most hydrophilic polyelectrolyte, PGLU.
Mitrakos
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Department of Chemistry, Erindale College, University of Toronto, Ontario, Canada.
Macdonald
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D000179:Acrylates / Q000737:chemistry; D000838:Anions; D002412:Cations; D004573:Electrolytes / Q000737:chemistry*; D008051:Lipid Bilayers / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D009829:Oleic Acids / Q000737:chemistry; D010713:Phosphatidylcholines / Q000737:chemistry; D011137:Polystyrenes / Q000737:chemistry; D011437:Propylamines / Q000737:chemistry; D012970:Sodium Glutamate / Q000737:chemistry; D013501:Surface-Active Agents / Q000737:chemistry
C090002:1,2-dioleoyl-3-(N,N-dimethylamino)propane; D000179:Acrylates; D000838:Anions; D002412:Cations; D004573:Electrolytes; D008051:Lipid Bilayers; D009829:Oleic Acids; D010713:Phosphatidylcholines; D011137:Polystyrenes; D011437:Propylamines; D013501:Surface-Active Agents; C003321:polystyrene sulfonic acid; C028694:1-palmitoyl-2-oleoylphosphatidylcholine; D012970:Sodium Glutamate