Spontaneous transformation of lamellar structures from simple to more complex states

Spontaneous transformation of lamellar structures, such as multilamellar vesicles from micelles or unilamellar vesicles, is an important challenge in the field of amphiphile molecules, which may serve as models to understand biologically relevant bilayer membranes. Herein, we report a progressive self-assembly progress of N-tetradecyllactobionamide (C14G2) and tetraethylene glycol monododecyl ether (C12EO4) mixtures in aqueous solution. Increasing temperature or surfactant compositions causes spontaneous transformation from simple to high-level aggregates, i.e., from unilamellar vesicles, to coexisting multilamellar vesicles, terraced planar bilayers, and finally terraced planar bilayers. Deuterium nuclear magnetic resonance ((2)H NMR), freeze-fracture transmission electron microscopy (FF-TEM), and small-angle X-ray scattering (SAXS) measurements clearly demonstrate the spontaneously progressive self-assembly process. The interlamellar spacing (d) of the bilayers decreases from unilamellar vesicles to the terraced planar bilayers with an increase of the temperature or surfactant compositions. Lamellar samples consisting of terraced planar bilayers at higher temperature still show viscoelastic properties, being Bingham fluids, and both the viscoelasticity and yield stress increase with the composition and decrease with the temperature. The spontaneous transformation of the progressive self-assembly progress of C14G2 and C12EO4 aqueous mixtures is due to a balance of three driving forces, hydrophobic interactions, hydrogen bonding, and steric effects.