Effect of chain unsaturation on bilayer response to pressure.

Using wide-line deuterium NMR, the effects of pressure on saturated-chain orientational order and gel-to-liquid-crystal phase transition temperature were observed in bilayers of 16:0-18:1 PC-d31 (POPC-d31) and 16:0-18:2 PC-d31 (PLPC-d31). Spectra were recorded for a range of pressures at selected temperatures and for a range of temperatures at selected pressures up to 193 MPa. For 16:0-18:1 PC-d31, the main transition temperature increased by approximately 0.18 K/MPa, a rate that is similar to what is found for bilayers of disaturated PC's. For 16:0-18:2 PC-d31, the increase in transition temperature with pressure was slightly smaller at approximately 0.13 K/MPa. To investigate the isothermal response of chain orientational order to pressure, spectra for each lipid were obtained for three pressures (ambient, 55 MPa, and 110 MPa) near room temperature (approximately 25 degrees C) and for three pressures (ambient, 110 MPa, and 193 MPa) at higher temperature (approximately 40 degrees C). These temperatures were chosen such that the difference between the higher observation temperature and the main transition of 16:0-18:1 PC-d31 would be similar to the difference between the lower observation temperature and the main transition of 16:0-18:2 PC-d31. Application of a given pressure was found to raise the orientational order for all methylene groups on the saturated chain of a particular lipid by roughly similar amounts. For comparable pressure differences, the pressure-induced ordering of the 16:0-18:1 PC-d31 saturated chain at approximately 40 degrees C was greater than that of the corresponding chain in 16:0-18:2 PC- d31 at approximately 25 degrees C. These observations suggest that increasing levels of chain unsaturation may reduce the sensitivity of bilayer order to variations in pressure at corresponding temperatures relative to their ambient pressure transitions.