Chemical exchange between lamellar and non-lamellar lipid phases. A one- and two-dimensional 31P-NMR study.
One- and two-dimensional 31P-exchange NMR has been used to investigate chemical exchange between coexisting lamellar (L alpha) and non-lamellar (hexagonal HII and cubic I2) lipid phases. Samples of DOPE, DOPE/DOPC (9:1 and 7:3), DOPE/cholesterol sulfate (9:1), DOPC/monoolein (MO) (3:7 and 1:1), and DOPC/DOPE/cholesterol (1:1:2) were macroscopically oriented on glass plates and studied at the 0 degree orientation (angle between the bilayer normal and the external magnetic field), where the L alpha, HII, and I2 resonances are resolved. A reversible L alpha to HII transition was observed for all of the samples except for the DOPC/MO mixtures, which displayed a reversible L alpha to I2 transition. Near-equilibrium mixtures of L alpha and either HII or I2 were obtained after prolonged incubation at a given temperature. Two-dimensional exchange experiments were performed on DOPE at 9-14 degrees C for mixing times ranging from 500 ms to 2 s. For all samples, one-dimensional exchange experiments were performed for mixing times ranging from 100 ms to 4 s, at temperatures ranging from 3 degrees C to 73 degrees C. No evidence of lipid exchange between lamellar and non-lamellar phases was observed, indicating that if such a process occurs it is either very slow on the seconds' timescale, or involves an undetectable quantity of lipid. The results place constraints on the stability or kinetic behaviour of proposed transition intermediates (Siegel, D.P. (1986) Biophys. J. 49, 1155-1170).
Fenske
D B
DB
Department of Biochemistry, Faculty of Medicine, University of British Columbia, Vancouver, Canada.
Cullis
P R
PR
D055598:Chemical Phenomena; D002627:Chemistry, Physical; D002788:Cholesterol Esters / Q000737:chemistry*; D005989:Glycerides / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D010713:Phosphatidylcholines / Q000737:chemistry; D010714:Phosphatidylethanolamines / Q000737:chemistry*; D013696:Temperature
D002788:Cholesterol Esters; D005989:Glycerides; D010713:Phosphatidylcholines; D010714:Phosphatidylethanolamines; C020888:1,2-dielaidoylphosphatidylethanolamine; C005953:monoolein; C017251:1,2-oleoylphosphatidylcholine; C007045:cholesteryl sulfate