Lipid Bilayer Phase Behavior - Physical Origins

Physical Origins

The phase behavior of lipid bilayers is largely determined by the strength of the attractive Van der Waals interactions between adjacent lipid molecules. The extent of this interaction is in turn governed by how long the lipid tails are and how well they can pack together. Longer tailed lipids have more area over which to interact, increasing the strength of this interaction and consequently decreasing the lipid mobility. Thus, at a given temperature, a short-tailed lipid will be more fluid than an otherwise identical long-tailed lipid. Another way of expressing this would be to say that the gel to liquid phase transition temperature increases with increasing number of carbons in the lipid alkane chains. Saturated phosphatidylcholine lipids with tails longer than 14 carbons are solid at room temperature, while those with fewer than 14 are liquid. This phenomenon is analogous to the fact that paraffin wax, which is composed of long alkanes, is solid at room temperature, while octane (gasoline), a short alkane, is liquid.

Aside from chain length, transition temperature can also be affected by the degree of unsaturation of the lipid tails. An unsaturated double bond can produce a kink in the alkane chain, disrupting the regular periodic structure. This disruption creates extra free space within the bilayer which allows additional flexibility in the adjacent chains. It is this disruption of packing that leads to lower transition temperatures with increasing double bonds. This is a particularly powerful effect; decreasing the overall chain length by one carbon usually alters the transition temperature of a lipid by ten degrees Celsius or less, but adding a single double bond can decrease the transition temperature by seventy degrees or more (see table). An example of this effect can be noted in everyday life as butter, which has a large percentage saturated fats, is solid at room temperature while vegetable oil, which is mostly unsaturated, is liquid.

Transition temperature (in °C) as a function of tail length and saturation. All data are for lipids with PC headgroups and two identical tails.
Tail Length Double Bonds Transition Temperature
12 0 -1
14 0 23
16 0 41
18 0 55
20 0 66
22 0 75
24 0 80
18 1 1
18 2 -53
18 3 -60

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