Effects of phospholipid acyl chain structure on thermotropic phase properties. 3. Phosphatidylcholines with (−), and (±)-anteiso acyl chains

We have synthesized a number of anteiso-branched fatty acids, both as racemates and as pure (?)-stereoisomers, as well as the corresponding di-anteiso-acyl phosphatidylcholines (PCs). The phase transition temperatures (_c of the hydrated PCs have been determined by differential thermal analysis (DTA). Consideration of the observed effects of acyl chain length and terminal see-butyl group configuration on anteiso acid melting points and di-anteiso-acyl PC transition temperatures leads us to the conclusion that the terminal branched portions of anteiso acyl chains interact only weakly with adjacent acyl chains in the hydrated phosphatidylcholine bilayer and probably in the anhydrous fatty acid crystal as well. In agreement with this conclusion, we observe that the DTA heating transition endotherms for hydrated di-anteiso-acyl PCs appear to be considerably less strongly endothermic, and occur at much lower temperatures, than do the major transition endotherms for the di-n-acyl PCs of like carbon number. Our findings generally support the proposal that anteiso acyl lipids tend to fluidize membranes, although they do so less effectively than do cis-unsaturated acyl lipids.     

Lipid oxidation and gel to liquid-crystalline transition temperatures of synthetic polyunsaturated mixed-acid phosphatidylcholines

Synthetic preparations of the polyunsaturated phosphatidylcholines 1-stearoyl-2-linoleoyl-sn-glycero-3-phosphocholine (SLPC) and 1-stearoyl-2-α-linolenoyl-sn-glycero-3-phosphocholine (SLnPC) were observed to undergo autooxidation sometimes during synthesis and also on storage. Oxidation was also induced by treatment of unoxidized SLPC with ultraviolet irradiation. Oxidation was estimated by thin layer chromatographic, fatty acid and ultraviolet spectral analyses. With limited oxidation, the gel to liquid-crystalline transition temperatures of aqueous dispersions of these lipids were seen to increase. Extensive oxidation led to a reduction in the enthalpies of the transitions. The increases in transition temperatures were consistent with the presence of conjugated double bonds, as shown by increased absorption at 230 nm, and trans double bonds, in the oxidized lipids leading to the creation of more rigid domains within the bilayer. Some of the changes in the transitions, especially the decreasing enthalpy after extensive oxidation, may have occurred because of the presence of small amounts of lysophosphatidylcholine and other oxidation intermediates or breakdown products seen by thin layer analysis. Thermograms of mixtures of unoxidized SLPC with amounts of lysostearoylPC found in the oxidized samples showed, however, that lysoPC likely did not contribute significantly to the increase in transition temperatures. Thin layer analysis suggested that the presence of cross-linked products could have contributed to the observed thermotropic properties.     

Interaction of biologically active molecules with phospholipid membranes: I. Fluorescence depolarization studies on the effect of polymeric biocide bearing biguanide groups in the main chain

Interaction of poly(hexamethylene biguanide hydrochloride) (PHMB), which is a polymeric biocide bearing biguanide groups in its main chain, with phospholipid bilayers was studied by the fluorescence depolarization method. A strong interaction of PHMB with negatively charged bilayers composed of phosphatidylglycerol(PG) alone or of PG and phosphatidylcholine (PC) was observed, whereas neutral PC bilayers were not affected. On adding PHMB, the fluorescence polarization of diphenylhexatriene embedded in the negatively charged bilayers was reduced to a great extent, especially in the gel phase. This was interpreted in terms of PHMB-induced expansion and fluidization of the bilayer, which enables the probe molecule to undergo less-hindered torsional motion. Similarity between PHMB and polymyxin B in the structure, the mode of action against bacteria and the interaction with lipid membranes is discussed.