Tuning the Helicity of Self-Assembled Structure of a Sugar-Based Organogelator by the Proper Choice of Cooling Rate

A novel sugar-appended low-molecular-mass gelator, 4 ''-butoxy-4-hydroxy-p-terphenyl-beta-D-glucoside (BHTG), was synthesized. It formed thermally reversible gels in a variety of aqueous and organic solvents. Three-dimensional networks made up of helical ribbons were observed in the mixture H2O/1,4-dioxane (40/60 v/v). The handedness of the ribbons depended on the rate of gel formation. Fast-cooling process led to right-handed ribbons, while slow-cooling process led to left-handed ones. A combinatory analyses of microscopic, spectroscopic, and diffraction techniques revealed that BHTG formed a twisted interdigitated bilayer structure with a d spacing of 3.1 nm in gels through a kinetically controlled nucleation-growth process. There were two kinds of molecular orientations of BHTG in the nuclei, clockwise and anticlockwise. which dictated the growth of ribbons. One was metastable and formed first during the cooling process of gel formation. It was able to gradually transform into the more stable latter one with decreasing temperature, Fast-cooling process did not leave enough time for the nuclei to evolve from transformed to stable state and the ribbons grown from them exhibited right-handedness. However, the metastable nuclei transformed into the stable one when cooled slowly and directed the molecules of BHTG to grow into left-handed aggregates.