Hydration and Molecular Motions in Synthetic Phytanyl-Chained Glycolipid Vesicle Membranes

Abstract

Proton permeation rates across membranes of a synthetic branch-chained glycolipid, 1,3-di- O-phytanyl-2- O-( β- d-maltotriosyl)glycerol (Mal 3(Phyt) 2) as well as a branch-chained phospholipid, diphytanoylphosphatidylcholine (DPhPC) were lower than those of straight-chained lipids such as egg yolk phosphatidylcholine (EPC) by a factor of ∼4 at pH 7.0 and 25°C. To examine whether degrees of water penetration and molecular motions in Mal 3(Phyt) 2 membranes can account for the lower permeability, nanosecond time-resolved fluorescence spectroscopy was applied to various membranes of branch-chained lipids (Mal 3(Phyt) 2, DPhPC, and a tetraether lipid from an extremely thermoacidophilic archaeon Thermoplasma acidophilum), as well as straight-chained lipids (EPC, 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC), and digalactosyldiacylglycerol (DGDG)) using several fluorescent lipids. Degrees of hydration of glycolipids, Mal 3(Phyt) 2, and DGDG were lower than those of phospholipids, EPC, POPC, and DPhPC at the membrane-water interfaces. DPhPC showed the highest hydration among the lipids examined. Meanwhile, rotational and lateral diffusive motions of the fluorescent phospholipid in branch-chained lipid membranes were more restricted than those in straight-chained ones. The results suggest that the restricted motion of chain segments rather than the lower hydration accounts for the lower proton permeability of branch-chained lipid membranes.