Self-assembly and thermal phase transition behavior of unsymmetrical bolaamphiphiles having glucose- and...

The thermal phase transition and self-assembly behaviors in water of the crystalline lamellar films prepared from unsymmetrical bolaamphiphiles, N-(2-aminoethyl)-N'-(beta-d-glucopyranosyl)-alkanediamide [1(n), n = 12, 14, 16, 17, 18, and 20], have been studied using differential scanning calorimetry, polarized light microscopy, variable-temperature (VT) X-ray diffraction (XRD), and VT-IR spectroscopy. The behavior allowed us to classify the bolaamphiphiles into two categories: short chain 1(n) (n = 12, 14, 16, and 17) and long chain 1(n) (n = 18 and 20). On heating, the films of the long chain 1(n) exhibited polymorphism of two crystal phases (Cr1 and Cr2) and one thermotropic mesophase (smectic). These phases proved to consist of unsymmetrical monolayer lipid membranes (MLMs), in which the molecules packed in a parallel fashion. On the other hand, the films of the short chain 1(n) gave a single crystal phase (Cr1) consisting of symmetrical MLMs with antiparallel molecular packing. Scanning transmission electron microscopy and atomic force microscopy revealed that the long chain 1(n) self-assembles in alkaline aqueous solutions to form nanotubes with 110-120 nm outer diameters, while the short chain 1(n) produces nanotapes with 80-250 nm widths. XRD and IR measurements revealed that the nanotubes consist of unsymmetrical MLMs, while the nanotapes consist of symmetrical MLMs. The molecular packing of the initial solid phase was essentially maintained even in the self-assemblies in water. The self-assembly process in water allowed the symmetrical MLM films of the short chain 1(n) to convert into the symmetrical MLM nanotapes. Similarly, the unsymmetrical MLM films of the long chain 1(n) were converted into the unsymmetrical MLM nanotubes.