Subgel transition in diluted vesicular DODAB dispersions

Abstract

We have characterized the lipid chain freezing in dilute aqueous vesicle dispersions of the cationic lipid dioctadecyldimethylammonium bromide (DODAB) using wide and small angle X-ray scattering, solid state NMR, DSC, turbidity and density measurements. The lipids freeze in two steps. Above 40 °C the chains are fluid and the lipids are in a so-called liquid-crystalline state. When cooling below 40 °C, the lipids form a gel phase where the chains stretch, the molecules are more densely packed and most molecular degrees of freedom are frozen, or at least dramatically slowed down. In the gel phase, the chain packing is still disordered, while the chain mobility is significantly reduced. From NMR data we further conclude that also the molecular rotational diffusion around the molecular long axis is quenched. Slow chain reorientation may occur, but then as individual reorientations of the separate chains. When cooling further below 36 °C, crystalline ordering of the chains is obtained, resulting in a further increased packing density. We refer to this state as the subgel phase. The transitions are reversible. However, the formation of the ordered subgel is very slow for temperatures near the melting point. In fact, the gel phase can be supercooled by almost 20 °C for considerable time. From analyzing this transition in terms of classical nucleation we obtain an estimate of the intra-bilayer interfacial tension between the gel phase and the growing subgel domains of 2 mN m⁻¹.