Rapid Phase Transitions of Thermotropic Glycolipid Quasicrystal and Frank-Kasper Mesophases: A Mechanistic Rosetta Stone.

Experimental results are presented that serve to lower the barrier for developing the science and technology of non-classical thermotropic glycolipid mesophases, which now include dodecagonal quasicrystal (DDQC) and Frank-Kasper (FK) A15 and σ mesophases that can be produced under mild conditions from a versatile class of sugar-polyolefin conjugates. By employing "alloys" comprised of mono- and disaccharide-polyolefin conjugates, and optionally with vitamin E as a small molecule phase modulator, we report the spontaneous formation of stable A15 mesophases at ambient temperature. We further document a rich thermotropic phase map that includes DDQC, A15, and σ mesophases of tunable periodicity that are connected through rapid thermotropic phase transitions as a function of increasing temperature in the order: liquid-like packing (LLP)→DDQC → A15→σ→ disorder. This first direct observation of a rapid thermotropic A15→σ phase transition provides support for a diffusionless martensitic process proceeding through strain-induced introduction of planar defects into the A15 lattice.

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

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.

Small-Molecule Modulation of Soft-Matter Frank-Kasper Phases: A Method for Adding Function to Form.

Incorporation of small amounts of α-tocopherol (vitamin E) in blends with the cellobiose-triazole-linked atactic poly(4-methyl-1-pentene) (CB-aPMP) sugar-polyolefin conjugate can be used to exert external control over thermotropic phase behavior and provide access to non-canonical soft matter Frank-Kasper A15 and σ phases. These results establish a paradigm that can be used for the further design and development of scalable quantities of soft matter FK phases of increased structural complexity and functional capability.

An Exceptionally Stable and Scalable Sugar-Polyolefin Frank-Kasper A15 Phase.

"One-component" soft material Frank-Kasper (FK) phases are an intriguing structural form of matter that possess periodically ordered structures arising from the self-reconfiguration and close packing of an initial assembly of identical "deformable" spheres into two or more size- or shape-distinct sets of particles. Significant challenges that must still be addressed to advance the field of soft matter FK phases further, however, include their rare and unpredictable occurrence, uncertain mechanisms of solid-state assembly, and low thermodynamic stability. Here we show that a readily-accessible sugar-polyolefin conjugate quantitatively produces an exceptionally stable solid-state FK A15 phase through a rapid and irreversible thermotropic order-order transition, which contrary to other prevailing proposed mechanisms, does not require mass transfer between particles or large structural reorganization in the bulk to establish unit cell non-equivalency. Our results provide the basis for a realistic strategy for obtaining practical and scalable quantities of a diverse range of sugar-polyolefin FK A15 phases with unique intrinsic physical properties and chemical reactivities not previously seen in such systems.