Membrane lipid

Major classes

Phospholipids

Phospholipids and glycolipids consist of two long, nonpolar (hydrophobic) hydrocarbon chains linked to a hydrophilic head group.

The heads of phospholipids are phosphorylated and they consist of either:

• Glycerol (and hence the name phosphoglycerides given to this group of lipids), or
• Sphingosine (e.g. sphingomyelin and ceramide).

Glycerol dialkyl glycerol tetraether (GDGT) is helping to study ancient environmental factors.

Glycolipids

The heads of glycolipids (glyco- stands for sugar) contain a sphingosine with one or several sugar units attached to it. The hydrophobic chains belong either to:

• two fatty acids (FA) – in the case of the phosphoglycerides, or
• one FA and the hydrocarbon tail of sphingosine – in the case of sphingomyelin and the glycolipids.

Galactolipids – monogalactosyl diglyceride (MGDG) and digalactosyl diglycreride (DGDG) form the predominant lipids in higher plant chloroplast thylakoid membranes; liposomal structures formed by total lipid extract of thylakoid membranes have been found sensitive to sucrose as it turns bilayers into micellar structures.

Fatty acids

The fatty acids in phospho- and glycolipids usually contain an even number, typically between 14 and 24, of carbon atoms, with 16- and 18-carbon being the most common. FAs may be saturated or unsaturated, with the configuration of the double bonds nearly always cis. The length and the degree of unsaturation of FAs chains have a profound effect on membranes' fluidity. Plant thylakoid membranes maintain high fluidity, even at relatively cold environmental temperatures, due to the abundance of 18-carbon fatty acyl chains with three double bonds, linolenic acid, as has been revealed by 13-C NMR studies.

Phosphoglycerides

In phosphoglycerides, the hydroxyl groups at C-1 and C-2 of glycerol are esterified to the carboxyl groups of the FAs. The C-3 hydroxyl group is esterified to phosphoric acid. The resulting compound, called phosphatidate, is the simplest phosphoglycerate. Only small amounts of phosphatidate are present in membranes. However, it is a key intermediate in the biosynthesis of the other phosphoglycerides.

Sphingolipids

Sphingosine is an amino alcohol that contains a long, unsaturated hydrocarbon chain. In sphingomyelin and glycolipids, the amino group of sphingosine is linked to FAs by an amide bond. In sphingomyelin the primary hydroxyl group of sphingosine is esterified to phosphoryl choline.

In glycolipids, the sugar component is attached to this group. The simplest glycolipid is cerebroside, in which there is only one sugar residue, either Glc or Gal. More complex glycolipids, such as gangliosides, contain a branched chain of as many as seven sugar residues.

Sterols

The best known sterol is cholesterol, which is found in humans. Cholesterol also occurs naturally in other eukaryote cell membranes. Sterols have a hydrophobic four-membered fused ring rigid structure, and a small polar head group.

Cholesterol is bio-synthesised from mevalonate via a squalene cyclisation of terpenoids. Cell membranes require high levels of cholesterol – typically an average of 20% cholesterol in the whole membrane, increasing locally in raft areas up to 50% cholesterol (- % is molecular ratio). It associates preferentially with sphingolipids (see diagram) in cholesterol-rich lipid rafts areas of the membranes in eukaryotic cells. Formation of lipid rafts promotes aggregation of peripheral and transmembrane proteins including docking of SNARE and VAMP proteins. Phytosterols, such as sitosterol and stigmasterol, and hopanoids serve a similar function in plants and prokaryotes.