title: Anion binding to neutral and positively charged lipid membranes.
abstract: Aqueous anion binding to bilayer membranes consisting of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) was investigated by using deuterium and phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy. Only those anions that exhibit chaotropic properties showed significant binding to POPC membranes. A detailed investigation of thiocyanate binding to neutral POPC and to positively charged mixed POPC/dihexadecyldimethylammonium bromide (DHDMAB) (8:2 mol/mol) membranes revealed changes in the 2H NMR quadrupole splittings from POPC specifically deuteriated at either the alpha-segment or the beta-segment of the choline head group which were consistent with a progressive accumulation of excess negative charge at the membrane surface with increasing SCN- concentration. Both the 2H and 31P NMR spectra indicated the presence of fluid lipids in a bilayer configuration up to at least 1.0 M NaSCN with no indication of any phase separation of lipid domains. Calibration of the relationship between the change in the 2H NMR quadrupole splitting and the amount of SCN- binding provided thiocyanate binding isotherms. At a given SCN- concentration the positively charged membranes bound levels of SCN- 3 times that of the neutral membranes. The binding isotherms were analyzed by considering both the electrostatic and the chemical equilibrium contributions to SCN- binding. Electrostatic considerations were accounted for by using the Gouy-Chapman theory. For 100% POPC membranes as well as for mixed POPC/DHDMAB (8:2 mol/mol) membranes the thiocyanate binding up to concentrations of 100 mM was characterized by a partition equilibrium with an association constant of K approximately 1.4 +/- 0.3 M-1.(ABSTRACT TRUNCATED AT 250 WORDS)
authors.affiliation: Department of Biophysical Chemistry, University of Basel, Switzerland.
authors.forename: P M
authors.initials: PM
authors.lastname: Macdonald
authors.forename: J
authors.initials: J
authors.lastname: Seelig
mesh_terms: D000838:Anions; D001665:Binding Sites; D004563:Electrochemistry; D066298:In Vitro Techniques; D007700:Kinetics; D008051:Lipid Bilayers; D009682:Magnetic Resonance Spectroscopy; D010713:Phosphatidylcholines; D000644:Quaternary Ammonium Compounds; D013861:Thiocyanates
chemical_list: D000838:Anions; D008051:Lipid Bilayers; D010713:Phosphatidylcholines; D000644:Quaternary Ammonium Compounds; D013861:Thiocyanates; C046417:dihexadecyldimethylammonium; C031760:thiocyanate; C028694:1-palmitoyl-2-oleoylphosphatidylcholine