Dynamics of the phosphate group in phospholipid bilayers. A 31P-1H transient Overhauser effect study

Abstract

Two recent studies have addressed the question of the dynamics of the phosphate in egg phosphatidylcholine multilayers by measurement and interpretation of 31P NMR spin-lattice relaxation. In the first (Milburn, M. P., and K. R. Jeffrey. 1987. Biophys. J. 52:791-799), the temperature dependences of the two contributions to the 31P relaxation rate, a dipolar interaction of the phosphorus with neighboring protons and a time-dependent anisotropic chemical shielding interaction were separately measured. A further study (Milburn, M. P., and K. R. Jeffrey. 1989. Biophys. J. 56:543-549) incorporated the anisotropic nature of phospholipid motions into the dynamic model of the headgroup motion by measuring the 31P spin-lattice relaxation time in oriented samples as a function of angle between the bilayer normal and the magnetic field. These angular dependent measurements were made at high field so that analysis could by made using the chemical shielding interaction because the 31P-1H dipolar interaction in phospholipid systems is complex and as such poorly understood. Nuclear Overhauser effect (NOE) studies have attempted to identify the important proton species contributing to the 31P-1H dipolar interaction (Yeagle, P. L., W. C. Hutton, C. Huang, and R. B. Martin. 1975. Biochemistry. 15:2121-2124) and despite some controversy in interpretation (Burns, R. A., R. E. Stark, D. A. Vidusek, and M. F. Roberts. 1983. Biochemistry. 22:5084-5090), it was generally agreed that the choline methyl and methylene protons are the major contributors to the 31P-1H NOE. To further understand the nature of the 31P-1H dipolar interaction, we carried out 31P-1H Transient Overhauser effect (TOE) measurements on egg phosphatidylcholine multilayers. Protons from both the lipids and water are important in understanding the TOE measurements in both D20 dispersions and H20 dispersions of egg PC. A quantitative analysis of the TOE has enabled the cross-relaxation rate between the phosphorus and the two proton types to be determined. It is suggested that these TOE experiments are a direct observation of the interaction between the phospholipid phosphate and surrounding water protons. The correlation time describing the relative motion of the phosphate group and the water molecules is on the order of 10- 11 s. The TOE measurements in phospholipid dispersions can be easily understood in terms of a straight forward model of the dipolar interaction and provide complementary information to NOE and T1 measurements.