Mixed-chain phospholipids: structures and chain-melting behavior.
It has long been established that diacyl phospholipids isolated from animal cell membranes are predominantly of a mixed-chain variety, meaning that the sn-1 and sn-2 acyl chains are saturated and unsaturated acyl chains, respectively. In general, monoenoic and dienoic acids are found in the sn-2 acyl chain of phosphatidylcholine (PtdCho), whereas polyenoic acids are in phosphatidylethanolamine (PtdEth). These unsaturated chains contain only cis-double bonds, which are always methylene-interrupted. In recent years, the structures and the chain-melting behavior of mixed-chain PtdCho and PtdEth have been systematically studied in this laboratory. Specifically, we have examined the effects of chain unsaturation of the sn-2 acyl chain on the phase transition temperature (Tm) of many PtdCho and PtdEth by high-resolution differential scanning calorimetry (DSC). The Tm values, for instance, obtained from all-unsaturated mixed-chain PtdEth derived from a common precursor can be grouped together according to their chemical formula to form a Tm-diagram. Hence, all the Tm values can be compared simply, systematically, and simultaneously using the Tm-diagram. In addition, the energy-minimized structures of mixed-chain phospholipids containing different numbers/positions of methylene-interrupted cis-double bonds have been simulated by molecular mechanics calculations (MM). In this review, the results of our MM and DSC studies carried out with various mixed-chain phospholipids are summarized. In addition, we emphasize that the combined approach of MM and DSC yields unique information that can correlate the various Tm-profiles seen in the Tm-diagram with the structural variation of mixed-chain lipids as caused by the introduction of different numbers/positions of methylene-interrupted cis-double bonds.
Huang
C H
CH
Department of Biochemistry and Molecular Genetics, University of Virginia School of Medicine, Charlottesville 22908, USA. ch9t@unix.mail.virginia.edu
D055598:Chemical Phenomena; D002627:Chemistry, Physical; D008958:Models, Molecular; D015394:Molecular Structure; D010713:Phosphatidylcholines / Q000737:chemistry; D010714:Phosphatidylethanolamines / Q000737:chemistry; D010743:Phospholipids / Q000737:chemistry*; D013329:Structure-Activity Relationship; D013816:Thermodynamics
D010713:Phosphatidylcholines; D010714:Phosphatidylethanolamines; D010743:Phospholipids