Lateral diffusion in sphingomyelin bilayers

• Sphingomyelin (SM) is an important lipid of eukaryotic cellular membranes and neuronal tissues. We studied lateral diffusion in macroscopically oriented bilayers of synthetic palmitoylSM (PSM) and natural sphingomyelins of egg yolk (eSM), bovine brain (bSM) and bovine milk (mSM) by NMR pulsed field gradient (NMR PFG) in the temperature range of 50-60oC. We found that the mean values of lateral diffusion coefficients (LDCs) of SMs are 1.9-fold lower in comparison with dipalmitoylphosphatidylcholine, which is similar in molecular structure. This discrepancy could be explained by the characteristics of intermolecular SM interactions. The LDCs of different SMs differ: egg SM is most similar to PSM, both of them have a 10% higher LDC value in comparison with the two other natural SMs. Besides, all natural SMs show a complicated form of the spin-echo diffusion decay, which is an indicator of a distribution of LDC values in bilayers. This peculiarity was explained by broad distributions of fatty acid lengths of the natural SMs studied here, especially mSM and bSM. We confirmed the relationship between chain length and the LDC in bilayers by computer analysis of a set of 1H NMR spectra obtained by scanning the value of the pulsed field gradient: there is a correlation between lower LDC values and SM molecules with longer acyl chains. The most probable mechanisms by which long-chain SM molecules decrease their lateral diffusion relative to the average value are protrusion into the other side of the bilayer or lateral separation into areas that diverge with their LDCs.

Ämnesord

NATURVETENSKAP  -- Kemi -- Fysikalisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Physical Chemistry (hsv//eng)

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Chemistry of Interfaces

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