A series of diphytanylglycerol phospholipids, i.e., diphytanylglycerol phosphate (PA), diphytanylglycerol phosphoglycerophosphate (PGP), the tri- and tetra-methyl derivatives of PGP, and the 2-deoxyglycerol analogue of PGP (dPGP) were studied by Fourier transform infrared spectroscopy. The use of the "deoxy" and methylated analogues of PGP, as well as that of PA and PGP of varying degrees of ionization, allowed the assignment of characteristic infrared bands associated with the phosphate groups. Analysis of these phosphate bands showed that at neutral pH, each of the two phosphate moieties in PGP is singly ionized, whereas in dPGP the phosphomonoester is doubly ionized. This is a consequence of the marked increase in the pK of one of the P-OH groups on the terminal phosphate of PGP (pK > 11), owing to the formation of an intramolecular hydrogen bond between the head group glycerol hydroxyl and the phosphate groups of PGP. Such an intramolecular hydrogen bond can not be formed by the dPGP analogue, and thus both negative charges in dPGP are located at the terminal phosphomonoester group. The O=P—OH groups of PGP also forms a network of intermolecular hydrogen bonds, the exact nature of which depends on concentration and degree of ionization. The possibility of a complex network of hydrogen bonds within (intramolecular) and between (intermolecular) anionic membrane lipids such as that found in PGP, is consistent with the hypothesis that these lipids function as proton-conducting pathways in membranes.Key words: phospholipids, infrared, hydrogen bonding, phosphatidylglycerophosphate, 2-deoxyphosphatidylglycerophosphate.
Separation of planar rotamers through intramolecular hydrogen bonding in polysubstituted 5-nitrosopyrimidines
