Influence of lipid lateral distribution on the surface charge response of the phosphatidylcholine headgroup as detected using 2H nuclear magnetic resonance.
The effect of lipid lateral distribution on the surface charge response of the phosphatidylcholine headgroup, in bilayers composed of binary mixtures of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 1,2-dimyristoyl-sn-glycero-3-phosphate (DMPA), was investigated by monitoring the deuterium nuclear magnetic resonance (2H-NMR) spectrum of choline-deuterated phosphatidylcholine as a function of temperature and DMPA concentration. Addition of DMPA at temperatures corresponding to fully liquid-crystalline membranes caused a progressive increase (decrease) in the 2H-NMR quadrupole splitting from POPC-alpha-d2 (POPC-beta-d2), in agreement with the known response of phosphatidylcholine to negative membrane surface charge (Seelig, J., Macdonald, P.M. and Scherer, P.G. (1987) Biochemistry 26, 7535-7541). Lateral phase separation of DMPA-rich domains was induced in these mixtures by lowering the temperature in the range from 60 degrees C to -15 degrees C, and was accompanied by a reversal of the original effects of DMPA on the quadrupole splitting. Analysis of the 2H-NMR spectral response allows one to generate a temperature/composition phase diagram for the POPC/DMPA system. We conclude that 2H-NMR of headgroup-deuterated phosphatidylcholine can be employed to sense and to quantify inhomogeneities in the lateral distribution of charged membrane components.
Marassi
F M
FM
Department of Chemistry, University of Toronto, Ontario, Canada.
Djukic
S
S
Macdonald
P M
PM
D000814:Aniline Compounds; D002152:Calorimetry, Differential Scanning; D003903:Deuterium; D009682:Magnetic Resonance Spectroscopy; D010713:Phosphatidylcholines / Q000737:chemistry*; D013696:Temperature
D000814:Aniline Compounds; D010713:Phosphatidylcholines; C050795:N,N-dimethyl-4-anisidine; D003903:Deuterium; C028694:1-palmitoyl-2-oleoylphosphatidylcholine