title: How do liquid mixtures solubilize insoluble gelators? Self-assembly properties of pyrenyl-linker-glucono gelators in tetrahydrofuran-water mixtures.
abstract: The self-assembly behavior of a series of glucono-appended 1-pyrenesulfonyl derivatives containing α,ω-diaminoalkane spacers (Pn, where n, the number of methylene units separating the amino groups, is 2, 3, 4, 6, 7, and 8) in v:v tetrahydrofuran (THF):water mixtures is examined at room temperature. The Pn at 2 w/v % concentrations do not dissolve in either THF or water at room temperature. However, the Pn can be dissolved in some THF:water mixtures, and they form gels spontaneously in other compositions without dissolving completely. The self-assembly of the Pn in the liquid mixtures has been investigated using a variety of techniques. The particle sizes of the Pn in their solutions/sols, critical gelation concentrations, microstructures, thermal and mechanical stabilities of the gels, and molecular packing modes of Pn molecules in their gel networks are found to be very dependent on the composition of the liquid mixtures. Correlations between the self-assembly behavior of the Pn and the polarity of the liquid mixtures, as probed by E(T)(30) and Hansen solubility parameters, yield both qualitative and quantitative insights into why self-assembly of the Pn can or cannot be achieved in different liquid compositions. As revealed by UV-vis and fluorescence spectroscopy studies, π-π stacking of the pyrenyl groups occurs as part of the aggregation process. Correlations between the rheological properties of the gels and the Hansen solubility parameters of the Pn and the solvent mixtures indicate that hydrogen-bonding interactions are a major contributor to the mechanical stability. Overall, the results of this study offer a new strategy to investigate the balance between dissolution and aggregation of molecular gelators. To the best of our knowledge, this is the first example of the spontaneous formation of molecular gels without heating by placing gelators in mixtures of liquids in which they are insoluble in the neat components.
authors.affiliation: Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P. R. China.
authors.forename: Ni
authors.initials: N
authors.lastname: Yan
authors.forename: Zhiyan
authors.initials: Z
authors.lastname: Xu
authors.forename: Kevin K
authors.initials: KK
authors.lastname: Diehn
authors.forename: Srinivasa R
authors.initials: SR
authors.lastname: Raghavan
authors.forename: Yu
authors.initials: Y
authors.lastname: Fang
authors.forename: Richard G
authors.initials: RG
authors.lastname: Weiss