2H NMR and polyelectrolyte-induced domains in lipid bilayers.
2H NMR studies of polyelectrolyte-induced domain formation in lipid bilayer membranes are reviewed. The 2H NMR spectrum of choline-deuterated phosphatidylcholine (PC) reports on any and all sources of lipid bilayer surface charge, since these produce a conformation change in the choline head group of PC, manifest as a change in the 2H NMR quadrupolar splitting. In addition, homogeneous and inhomogeneous surface charge distributions are differentiated. Adding polyelectrolytes to lipid bilayers consisting of mixtures of oppositely charged and zwitterionic lipids produces 2H NMR spectra which are superpositions of two Pake sub-spectra: one corresponding to a polyelectrolyte-bound lipid population and the other to a polyelectrolyte-free lipid population. Quantitative analysis of the quadrupolar splittings and spectral intensities of the two sub-spectra indicate that the polyelectrolyte-bound populations is enriched with oppositely charged lipid, while the polyelectrolyte-free lipid population is correspondingly depleted. The same domain-segregation effect is produced whether cationic polyelectrolytes are added to anionic lipid bilayers or anionic polyelectrolytes are added to cationic lipid bilayers. The 2H NMR spectra permit a complete characterization of domain composition and size. The anion:cation ratio within the domains is always stoichiometric, as expected for a process driven by Coulombic interactions. The zwitterionic lipid content of the domains is always statistical, reflecting the systems tendency to minimize the entropic cost of demixing charged lipids into domains. Domain formation is observed even with rather short polyelectrolytes, suggesting that individual polyelectrolyte chains aggregate at the surface to form "superdomains". Overall, the polyelectrolyte bound at the lipid bilayer surface appears to lie flat along the surface and to be essentially immobilized through its multiple electrostatic contacts.
Macdonald
P M
PM
Department of Chemistry, University of Toronto at Mississauga, Ontario, Canada. pmacdona@credit.erin.utoronto.ca
Crowell
K J
KJ
Franzin
C M
CM
Mitrakos
P
P
Semchyschyn
D
D
D000952:Antigens, Polyomavirus Transforming; D002411:Cation Exchange Resins; D000077286:Cetrimonium; D002593:Cetrimonium Compounds; D003902:Detergents; D003903:Deuterium; D004573:Electrolytes; D005229:Fatty Acids, Monounsaturated; D005456:Fluorescent Dyes; D008051:Lipid Bilayers; D009682:Magnetic Resonance Spectroscopy; D008970:Molecular Weight; D010713:Phosphatidylcholines; D010715:Phosphatidylglycerols; D011137:Polystyrenes; D000644:Quaternary Ammonium Compounds
D000952:Antigens, Polyomavirus Transforming; D002411:Cation Exchange Resins; D002593:Cetrimonium Compounds; D003902:Detergents; D004573:Electrolytes; D005229:Fatty Acids, Monounsaturated; D005456:Fluorescent Dyes; D008051:Lipid Bilayers; D010713:Phosphatidylcholines; D010715:Phosphatidylglycerols; D011137:Polystyrenes; D000644:Quaternary Ammonium Compounds; C003321:polystyrene sulfonic acid; C060037:1-palmitoyl-2-oleoylglycero-3-phosphoglycerol; D003903:Deuterium; C070046:1,2-dioleoyloxy-3-(trimethylammonium)propane; C028694:1-palmitoyl-2-oleoylphosphatidylcholine; D000077286:Cetrimonium