INVESTIGATION OF SOLID-STATE SELF-ASSEMBLY OF ONE- AND MULTI- COMPONENT SUGAR POLYOLEFIN CONJUGATES AND MECHANISMS FOR FRANK-KASPER MESOPHASE TRANSITIONS

Abstract

The self-assembly of molecules provides the basis of life and has become ubiquitous for the development of nanostructured materials. Nanostructured materials have long reaching impacts for the furtherment of science, as the next revolution in technology requires the ability to fabricate nanostructured materials with sub-10-nm feature sizes. To this end, the work herein, presents on methods and mechanisms of solid-state nanostructured mesophase formation, through the isolation of complex phases and understanding of thermotropic order-order transition pathways. This extends to both solid-state classical and nonclassical phases, including the highly desirable, bicontinuous double gyroid, and uncommon Frank-Kasper (FK) phases resulting from self-assembly of the sugar polyolefin conjugates. The sugar polyolefin conjugates are produced through practical and scalable bulk quantities that demonstrate the dynamic self-assembly on the nanometer-scale, which results from rapid thermally induced order-order phase transitions. Production of different derivatives of the sugar polyolefin conjugates and blended systems, can significantly lower the barriers to access uncommon and complex mesophases through the elucidation of transition mechanisms for FK mesophases. To better understand the basic principles and mechanisms of formation that result in the complex packing motifs of FK phases, single- and multi-component systems were devised. These mechanisms avoid the need for large structural reconfigurations of spheres, and dynamic mass transfer, as previous solid-state thermotropic mechanisms have required. Additionally, a general strategy for design, modulation, and utilization of functionally competent soft matter solid-state FK phases is provided from developments with a two-component system utilizing a small molecule additive. These results demonstrate the sugar polyolefin conjugates as an exceptional class of self-assembling amphiphilic materials, which provide methods for reliably producing Frank-Kasper phases from single- and multi-component systems, in addition to remarkable classical phase behavior.