title: Supramolecular helical nanofibers assembled from a pyridinium-functionalized methyl glycyrrhetate amphiphile.
abstract: A glycyrrhetate-containing amphiphile, MGP (1-[2-(methyl glycyrrhetate)-2-oxoethyl]pyridinium bromide), has been synthesized, and found to assemble into supramolecular helical nanofibers in chloroform/aromatic solvents, which are primarily driven by π-π stacking, van der Waals forces, and hydrophobic interactions. During the assembly process, MGP stacked into J-aggregates resulting in the sequestration of the hydrophilic pyridinium cation within the interior with the concomitant projection of its hydrophobic skeleton on the outside surface. Ultimately, this protrusion generated a staggered angle due to the steric hindrance between stacked molecules. This staggered angle further led to molecular misalignments and the formation of helical fibrils, which could twist with each other to fabricate larger helical fibers. Consequently, a gel was formed by intertwining these nanofibers into three-dimensional networks. Using this strategy, we found that other triterpenoid-tailored pyridinium amphiphiles are also potential scaffolds for supramolecular helical structures. This work provides a facile approach for the fabrication of supramolecular macroscopic chiral nanostructures that originate from natural products.
authors.affiliation: Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China. juyong@tsinghua.edu.cn.
authors.forename: Yuxia
authors.initials: Y
authors.lastname: Gao
authors.forename: Jie
authors.initials: J
authors.lastname: Hao
authors.forename: Jindan
authors.initials: J
authors.lastname: Wu
authors.forename: Xun
authors.initials: X
authors.lastname: Zhang
authors.forename: Jun
authors.initials: J
authors.lastname: Hu
authors.forename: Yong
authors.initials: Y
authors.lastname: Ju
mesh_terms: D006034:Glycyrrhetinic Acid / Q000737:chemistry*; D057139:Nanofibers / Q000737:chemistry* / Q000648:ultrastructure*; D011726:Pyridinium Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D011726:Pyridinium Compounds; D006034:Glycyrrhetinic Acid