A study of the headgroup motion of sphingomyelin using 31P NMR and an analytically soluble model. 2005

I C Malcolm, and J C Ross, and J Higinbotham
School of Mathematical and Physical Sciences, Napier University, 10 Colinton Road, Edinburgh, Scotland EH10 5DT, UK. ianmalcolm@beeb.net

A 31P NMR investigation has been carried out of the headgroup dynamics of sphingomyelin molecules in bilayers for the L alpha and L beta' phases. The resulting line shapes have been analysed in terms of a reduced-parameter model, using van Faassen's method for obtaining an analytic solution to first-order stochastic differential equations to simulate the line shapes of oriented and non-oriented samples. Our treatment results in good fits to measured data but using fewer parameters than traditional methods. Angles and correlation times (tau parallel and tau perpendicular) describing the geometry and dynamics of the headgroup are obtained by optimising the agreement between simulated and experimental data. The results are contrasted with those obtained for the lecithins DMPC and DPPC using a similar analysis. Not only are tau parallel and tau perpendicular now equal in value for the L alpha phase, but this value is also found to be nearly four times larger than the longest correlation time for the lecithins. We interpret this as evidence of inter- and intramolecular hydrogen bonding in the L(alpha) phase of sphingomyelin. In the L beta' phase of sphingomyelin, however, although tau(parallel) and tau(perpendicular) remain equal their value is now 32% smaller than that of the lecithins in the same phase. This indicates less difference between the fluidities in the headgroup region of the two phases of sphingomyelin as compared to that of the lecithins. Another significant difference between the L beta' phases is that the tilt angle for sphingomyelin is found to be nearly twice as large as for the lecithins. We argue that these combined observations point to the existence of hydrogen bonding in this phase also. Again in contrast to our previous work on lecithins, our results provide evidence of a negative diamagnetic anisotropy in sphingomyelin molecules, even in the L beta' phase. This is provided for in our model by the assumption that our unoriented samples consist of prolate ellipsoidal liposomes whose major axes are oriented parallel to the static magnetic field. The apparently different diamagnetic behaviour of sphingomyelin in the present work is due to the higher static field used rather than any intrinsic difference in this respect between sphingomyelin and the lecithins DMPC and DPPC.

UI MeSH Term Description Entries
D008051 Lipid Bilayers Layers of lipid molecules which are two molecules thick. Bilayer systems are frequently studied as models of biological membranes. Bilayers, Lipid,Bilayer, Lipid,Lipid Bilayer
D009682 Magnetic Resonance Spectroscopy Spectroscopic method of measuring the magnetic moment of elementary particles such as atomic nuclei, protons or electrons. It is employed in clinical applications such as NMR Tomography (MAGNETIC RESONANCE IMAGING). In Vivo NMR Spectroscopy,MR Spectroscopy,Magnetic Resonance,NMR Spectroscopy,NMR Spectroscopy, In Vivo,Nuclear Magnetic Resonance,Spectroscopy, Magnetic Resonance,Spectroscopy, NMR,Spectroscopy, Nuclear Magnetic Resonance,Magnetic Resonance Spectroscopies,Magnetic Resonance, Nuclear,NMR Spectroscopies,Resonance Spectroscopy, Magnetic,Resonance, Magnetic,Resonance, Nuclear Magnetic,Spectroscopies, NMR,Spectroscopy, MR
D010759 Phosphorus Isotopes Stable phosphorus atoms that have the same atomic number as the element phosphorus, but differ in atomic weight. P-31 is a stable phosphorus isotope. Isotopes, Phosphorus
D004134 Dimyristoylphosphatidylcholine A synthetic phospholipid used in liposomes and lipid bilayers for the study of biological membranes. Dimyristoyllecithin,1,2-Dimyristoyl-glycero-3-phosphorylcholine,1,2-Ditetradecanoyl-glycero-3-phosphocholine,1,2-Ditetradecyl-glycero-3-phosphocholine,DMCP,DMPC,1,2 Dimyristoyl glycero 3 phosphorylcholine,1,2 Ditetradecanoyl glycero 3 phosphocholine,1,2 Ditetradecyl glycero 3 phosphocholine
D013109 Sphingomyelins A class of sphingolipids found largely in the brain and other nervous tissue. They contain phosphocholine or phosphoethanolamine as their polar head group so therefore are the only sphingolipids classified as PHOSPHOLIPIDS. Sphingomyelin
D015060 1,2-Dipalmitoylphosphatidylcholine Synthetic phospholipid used in liposomes and lipid bilayers to study biological membranes. It is also a major constituent of PULMONARY SURFACTANTS. Dipalmitoyllecithin,1,2-Dihexadecyl-sn-Glycerophosphocholine,1,2-Dipalmitoyl-Glycerophosphocholine,Dipalmitoyl Phosphatidylcholine,Dipalmitoylglycerophosphocholine,Dipalmitoylphosphatidylcholine,1,2 Dihexadecyl sn Glycerophosphocholine,1,2 Dipalmitoyl Glycerophosphocholine,1,2 Dipalmitoylphosphatidylcholine,Phosphatidylcholine, Dipalmitoyl
D015394 Molecular Structure The location of the atoms, groups or ions relative to one another in a molecule, as well as the number, type and location of covalent bonds. Structure, Molecular,Molecular Structures,Structures, Molecular
D016880 Anisotropy A physical property showing different values in relation to the direction in or along which the measurement is made. The physical property may be with regard to thermal or electric conductivity or light refraction. In crystallography, it describes crystals whose index of refraction varies with the direction of the incident light. It is also called acolotropy and colotropy. The opposite of anisotropy is isotropy wherein the same values characterize the object when measured along axes in all directions. Anisotropies

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