2H nuclear magnetic resonance order parameter profiles suggest a change of molecular shape for phosphatidylcholines containing a polyunsaturated acyl chain.
Solid-state 2H nuclear magnetic resonance spectroscopy was used to determine the orientational order parameter profiles for a series of phosphatidylcholines with perdeuterated stearic acid, 18:0d35, in position sn-1 and 18:1 omega 9, 18:2 omega 6, 18:3 omega 3, 20:4 omega 6, 20:5 omega 3, or 22:6 omega 3 in position sn-2. The main phase transition temperatures were derived from a first moment analysis, and order parameter profiles of sn-1 chains were calculated from dePaked nuclear magnetic resonance powder patterns. Comparison of the profiles at 37 degrees C showed that unsaturation causes an inhomogenous disordering along the sn-1 chain. Increasing sn-2 chain unsaturation from one to six double bonds resulted in a 1.6-kHz decrease in quadrupolar splittings of the sn-1 chain in the upper half of the chain (or plateau region) and maximum splitting difference of 4.4 kHz at methylene carbon 14. The change in chain order corresponds to a decrease in the 18:0 chain length of 0.4 +/- 0.2 A with 18:2 omega 6 versus 18:1 omega 9 in position sn-2. Fatty acids containing three or more double bonds in sn-2 showed a decrease in sn-1 chain length of 0.7 +/- 0.2 A compared with 18:1 omega 9. The chain length of all lipids decreased with increasing temperature. Highly unsaturated phosphatidylcholines (three or more double bonds in sn-2) had shorter sn-1 chains, but the chain length was somewhat less sensitive to temperature. The profiles reveal that the sn-1 chain exhibits a selective increase in motional freedom in a region located toward the bottom half of the chain as sn-2 unsaturation is increased. This corresponds to an area increase around carbon atom number 14 that is three to four times greater than the increase for the top part of the chain. A similar asymmetric decrease in order, largest toward the methyl end of the chain, was observed when 1 -palmitoyl-2-oleoylphosphatidylethanolamine goes from a lamellar to an inverse hexagonal (H,,) phase. This is consistent with a change to a more wedge-shaped space available for the acyl chain.
Holte
L L
LL
Section of NMR Studies, NIAAA, National Institutes of Health, Rockville, Maryland 20852, USA.
Peter
S A
SA
Sinnwell
T M
TM
Gawrisch
K
K
D003903:Deuterium; D005231:Fatty Acids, Unsaturated; D008051:Lipid Bilayers; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D008968:Molecular Conformation; D010713:Phosphatidylcholines / Q000737:chemistry*; D013329:Structure-Activity Relationship; D013816:Thermodynamics
D005231:Fatty Acids, Unsaturated; D008051:Lipid Bilayers; D010713:Phosphatidylcholines; D003903:Deuterium