Stable Thermotropic 3D and 2D Double Gyroid Nanostructures with Sub-2-nm Feature Size from Scalable Sugar-Polyolefin Conjugates.

Abstract

Ultra-low molecular weight disaccharide-polyolefin conjugates with cellobiose, lactose and maltose head groups and atactic polypropene tails, such as 1, undergo a series of irreversible thermotropic order-order transitions with increasing temperature to provide nanostructured phases in the sequence: lamellar (L), hexagonal perforated lamellar (HPL), double gyroid (DG) and hexagonal cylindrical (C). The DG phase displays exceptional stability at ambient temperature and features two interpenetrating sugar domain networks having a sub-2-nm strut width and a lattice parameter, aDG , of 13.1 nm. The unique stability of this DG phase extends further within ultrathin films all the way down to the two-dimensional limit of 15 nm in which film thickness, l, is now less than the surface-oriented unit cell height, hDG . In addition to raising the fundamental question of what minimally constitutes a Schoen triply periodic minimal surface and DG lattice, these results serve to establish the class of sugar-polyolefin conjugates as a new material platform for nanoscience and nanotechnology.