title: Stereochemical control of nonamphiphilic lyotropic liquid crystals: chiral nematic phase of assemblies separated by six nanometers of aqueous solvents.
abstract: Unlike conventional thermotropic and lyotropic liquid crystals, nonamphiphilic lyotropic liquid crystals consist of hydrated assemblies of nonamphiphilic molecules that are aligned with a separation of about 6 nm between assemblies in an aqueous environment. This separation raises the question of how chirality, either from chiral mesogens or chiral dopants, would impact the phase as the assemblies that need to interact with each other are about 6 nm apart. Here, we report the synthesis of three stereoisomers of disodium chromonyl carboxylate, 5'DSCG-diviol, and the correlation between the molecular structure, bulk assembly, and liquid crystal formation. We observed that the chiral isomers (enantiomers 5'DSCG-(R,R)-diviol and 5'DSCG-(S,S)-diviol) formed liquid crystals while the achiral isomer 5'DSCG-meso-diviol did not. Circular dichroism indicated a chiral conformation with bisignate cotton effect. The nuclear Overhauser effect in proton NMR spectroscopy revealed conformations that are responsible for liquid crystal formation. Cryogenic transmission electron microscopy showed that chiral 5'DSCG-diviols form assemblies with crossings. Interestingly, only planar alignment of the chiral nematic phase was observed in liquid crystal cells with thin spacers. The homeotropic alignment that permitted a fingerprint texture was obtained only when the thickness of the liquid crystal cell was increase to above ~500 μm. These studies suggest that hydrated assemblies of chiral 5'DSCG-diviol can interact with each other across a 6 nm separation in an aqueous environment by having a twist angle of about 0.22° throughout the sample between the neighboring assemblies.
authors.affiliation: Department of Chemistry, Syracuse University, Syracuse, New York 13244, USA.
authors.forename: Sijie
authors.initials: S
authors.lastname: Yang
authors.forename: Bing
authors.initials: B
authors.lastname: Wang
authors.forename: Dawei
authors.initials: D
authors.lastname: Cui
authors.forename: Deborah
authors.initials: D
authors.lastname: Kerwood
authors.forename: Stephan
authors.initials: S
authors.lastname: Wilkens
authors.forename: Junjie
authors.initials: J
authors.lastname: Han
authors.forename: Yan-Yeung
authors.initials: YY
authors.lastname: Luk
mesh_terms: D002942:Circular Dichroism; D004205:Cromolyn Sodium / Q000737:chemistry; D050866:Liquid Crystals / Q000737:chemistry*; D010316:Particle Size; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D004205:Cromolyn Sodium