Polymorphic phase preferences of phosphatidic acid: A 31P and 2H NMR study

31P NMR, 2H NMR and freeze fracture techniques have been employed to investigate the structural preferences of dioleoyl phosphatidic acid (DOPA) under various conditions of pH and divalent cation content. It is shown that DOPA increasingly prefers the HII organization below pH 5, and that low levels of Ca2+ and Mg2+ (Me2+/DOPA = 0.5) induce HII phase structure for pH less than 6.0. Higher Mg2+ and Ca2+ levels (Me2+/DOPA greater than 1.0) induce more complex structures at pH greater than 5.0 which may correspond to intermediates between lamellar and HII organization. This work illustrates the utility of 2H NMR techniques in conjunction with suitable 2H labelled lipids to provide structural information on lipid-water systems, and suggests that 31P NMR techniques for determinations of lipid organization can be applied to advantage in PA containing membranes.