New phases induced by sucrose in saturated phosphatidylethanolamines: an expanded lamellar gel phase and a cubic phase

摘要

A new lamellar gel phase (Lβ) with expanded lamellar period was found at low temperatures in dihexadecylphosphatidylethanolamine (DHPE) and dipalmitoylphosphatidylethanolamine (DPPE) dispersions in concentrated sucrose solutions (1–2.4 M). It forms via a cooperative, relatively broad transition upon cooling of the Lβ gel phase of these lipids. According to the X-ray data, the transformation between Lβ and Lβ is reversible, with a temperature hysteresis of 6–10°C and a transition width of about 10°C. No specific volume changes and a very small heat absorption of about 0.05 kcal/mol accompany this transition. The Lβ−Lβ transition temperature strongly depends on the disaccharide concentration. From a value of about 10°C below the melting transition of DHPE, it drops by 25°C with decrease of sucrose concentration from 2.4 M to 1 M. The low-temperature gel phase Lβ has a repeat spacing by 8–10 Å larger than that of the Lβ gel phase and a single symmetric 4.2 Å wide-angle peak. It has been observed in 1. 1.25, 1.5 and 2.4 M solutions of sucrose, but not in 0.5 M of sucrose. The data clearly indicate that the expanded lamellar period of the Lβ phase results from a cooperative, reversible with the temperature, increase of the interlamellar space of the Lβ gel phase. Other sugars (trehalose, maltose, fructose, glucose) induce similar expanded low-temperature gel phases in DHPE and DPPE. The Lβ phase is osmotically insensitive. Its lamellar period does not depend on the sucrose concentration, while the lattice spacings of the Lα, Lβ and HH phases decrease linearly with increase of sucrose concentration. Another notable sugar effect is the induction of a cubic phase in these lipids. It forms during the reverse HH−Lα phase transition and coexists with the Lα phase in the whole temperature range between the HH and Lβ phases. The cubic phase has only been observed at sucrose concentrations of 1 M and above. In accordance with previous data, sucrose suppresses the Lα phase in both lipids and brings about a direct Lβ−HH phase transition in DHPE. A rapid, reversible gel-subgel transformation takes place at about 17°C in both DPPE and DHPE. Its properties do not depend on the sucrose concentration. The observed new effects of disaccharides on the properties of lipid dispersions might be relevant to their action as natural protectants.