Structure of polymerizable lipid bilayers IV: mixtures of long chain diacetylenic and short chain saturated phosphatidylcholines and analogous asymmetric isomers

Abstract

Polymerization of 1,2-bis(tricosa-10,12-diynoyl)- sn-glycero-3-phosphocholine (DC 8,9PC) is enhanced by addition o short-chain saturated phosphatidylcholines such as 1,2-dinonanoyl- sn-glycero-3-phosphocholine (DNPC). Because of well established constraints on the topochemical polymerisation process, we undertook structure-based experiments to determine the nature of this effect. Two hypotheses were tested: (a) that the DNPC crystalized the proximal ( m) and disordered the distal ( n) methylene segments of DC 8,9PC, thus providing flexibility to accommodate the conformational change upon polymer formation, or (b) that the DNPC forced lateral displacement of DC 8,9PC, which would then allow interdigitation of these segments with those of the opposing monolayer and potentially more crystalline alignment of the diacetylene. Low angle X-ray diffraction studies do not support the interdigiated chain model. However, these measurements also indicate that the two lipid species may be phase separated under many conditions. An analogous structure, 1-(tricosa-10,12-diynoyl)2-nonanoyl- sn-glycero-3-phosphocholine (C 8,9NPC) did not polymerize, and low angle X-ray diffraction studies indicate that bilayers of this lipid were interdigitated such that the terminal methyl group of the tricosadiynoyl chain on each lipid in the bilayer was adjacent to the diacetylenic moiety of a lipid on the opposing monolayer. Implications of these findings pertinent to identifying significant factors in polymerization of diacetylenic phospholipid bilayers are discussed.