Oligomer-to-polymer transition in short ethylene glycol chains connected to mobile hydrophobic anchors.

We studied the structure of short ethylene glycol (EG) chains with N repeating units (EGN, N = 3, 6, 9, 12, and 15) connected to hydrophobic dihexadecyl chains by means of a combination of differential scanning calorimetry (DSC) and small- and wide-angle X-ray scattering (SAXS/WAXS). These synthetic amphiphiles dispersed in water form planar lamellar stacks and hexagonal cylinders confining the EG chains to restricted geometries. Owing to the self-assembly of the anchoring points, the lateral density of EG chains in planar lamella can be quantitatively controlled. Furthermore, the chain-melting phase transition of the anchors enables us to "switch" the intermolecular distance reversibly. SAXS/WAXS results suggest that the shorter EG chains (N = 3, 6, and 9) assume a helical conformation in stacks of planar lamella. When the EG chains are further elongated (N = 12 and 15), the lamellar periodicities cannot be explained by a linear extrapolation of shorter oligomers, but can be interpreted well as polymer brushes following the scaling theorem. Such rich phase behaviors of EGN molecules can be used as a simple model of oligo/poly-saccharide chains on cell surfaces, which act not only as flexible repellers between neighboring cells but also as stable spacers for functional ligands.