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

• Published in: Angewandte Chemie (International ed.) 2021-04, Vol.60 (16), p.8710-8716
• Main Authors: Nowak, Samantha R., Lachmayr, Kätchen K., Yager, Kevin G., Sita, Lawrence R.
• Format: Article
• Language: English
• Subjects: Ambient temperature; Cellobiose; Conjugates; Disaccharides; Film thickness; gyroid; Interpenetrating networks; Lactose; Low molecular weights; Maltose; Minimal surfaces; Molecular weight; Nanotechnology; Polyolefins; self-assembly; Stability; Sugar; Thin films; ultrathin film; Unit cell
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202016384

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. Ultra‐low molecular weight disaccharide–polyolefin conjugates with cellobiose, lactose and maltose head groups and atactic polypropene tails, such as 1, provide highly ordered and exceptionally stable thermotropic hexagonal perforated lamellar (HPL) and double gyroid (DG) nanostructured phases. The unique stability of this DG phase extends further 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.