The 2H-NMR spectra of selectively deuterated cholesterol, intercalated in egg phosphatidylcholine, were examined. The orientation of the axis of motional averaging was calculated using the observed quadrupole splittings and the atomic coordinates. With the known orientation of the rotation axis, qua
Direct observation of the properties of cholesterol in membranes by deuterium NMR
β Scribed by Michael G. Taylor; Toshiyuki Akiyama; Hazime Saito; Ian C.P. Smith
- Publisher
- Elsevier Science
- Year
- 1982
- Tongue
- English
- Weight
- 986 KB
- Volume
- 31
- Category
- Article
- ISSN
- 0009-3084
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β¦ Synopsis
The properties of cholesterol in bilayers of egg phosphatidylchollne (PC) were investigated directly by means of aH-NMR of specffically-deuterated species (C3, C7, C26, C27). Quadrupole splittings were a measure of molecular ordering, and relaxation times T, and T2e were indicators of rates of motion. The importance of the use of echoes for spectral acquisition is emphasised, particularly to obtain accurate values of the quadrupole splitting. In the ease of overlapping powder patterns from two labelled positions, the use of the absolute value mode of spectral presentation is shown to yield reasonable estimates of the individual quadrupoie splittings. Spectral properties were monitored as a function of cholesterol concentration and temperature. Increasing cholesterol concentration led to a high degree of ordering for the rigid ring system of cholesterol, approaching a molecular order parameter of 0.8 at 50 reel% cholesterol. The isopropyl methyl groups were in all cases less ordered and more mobile than the ring system, but responded in a similar fashion to variable cholesterol concentration and temperature. The observation of a minimum in the temperature dependence of T 1 for cholesterol-7,7~/ 2 led to a direct estimate of its correlation time for molecular motion, 3.5 Γ 10 -9 s rad-L This indicates that the overall rate of motion of cholesterol is considerably slower than that of the lipids in which it is located. The short T2e values suggest that the motional spectrum of cholesterol is rich in low frequencies. The parallel temperature and cholesterol dependences of quadrupole splittings for different positions on the rigid ring system of cholesterol indicate that the position of the axis of motional averaging of the molecule is not changing, and is the same as that determined in an earlier study, It is emphasised that the steep temperature dependence and small quadrupole splittings for the chain isopropyl methyl groups of cholesterol do not necessarily indicate a high degree of disorder, but may be due to their axes of motional averaging lying at angles close to 54 Β° with respect to the director of the ordered lipids.
π SIMILAR VOLUMES
Spin-lattice relaxation, T1z, measurements of [2,2,3,4,4,6-2H6]cholesterol in model membranes of DMPC were performed as a function of temperature, Larmor frequency and position of labelling in the fused ring system. The results are interpreted according to a hierarchy of motions, such that motion i
## Abstract Mixtures of cholesterol with phosphatidylcholine species containing the polyunsaturated acyl chains arachidonoyl or docosahexaenoyl were studied by ^13^C magic angle spinning (MAS) NMR using both crossβpolarization and direct polarization, by ^31^P NMR and by differential scanning calor