Exploring the Self-assembly of Glycolipids into Three-dimensional Network Phases

Glycolipids are intriguing molecules comprising a glycan head group and a lipid moiety, which self-assemble into a number of ordered phases. Their ability to form 3D network phases, such as double gyroid and double diamond, has drawn much attention due to their useful bicontinuous structures. However, the specific inter- and intra- molecular interactions underlying this useful self-assembly behavior remain obscure. In this work, we developed a molecular dynamics simulation workflow to predict the formation of network phases in glycolipids for concurrent experimental studies. Specifically, a multi-step simulation strategy featuring a guiding-field method was used to investigate the stability of four network structures, including double gyroid, double diamond, single gyroid and single plumber’s nightmare (single primitive). The two Guerbet glycolipids, disaccharide-based β-maltose-C₁₄C₁₀ and monosaccharide-based β-galactose-C₁₄C₁₀, are thus shown to exhibit distinct phase behavior. Their predicted thermotropic liquid crystalline phase behavior is corroborated by experimental results based on small-angle X-ray scattering of analytically pure samples of these glycolipids.