Columnar molecular aggregation in the aqueous solutions of disodium cromoglycate

Stack, chimneylike, and threadlike assemblies have previously been proposed for the structure of disodium cromoglycate (DSCG) aggregates in aqueous solutions. The results of the synchrotron x-ray scattering investigations reported here reveal the formation of simple columnar assemblies with pi-pi stacking at a separation of 3.4 angstrom between the DSCG molecules. Lateral separation between the assemblies is concentration and temperature dependent, varying from similar to 35 to 42 angstrom in the orientationally ordered nematic (N) phase and from 27 to 32 angstrom in the columnar or middle (M) phase having long range lateral positional order. The assemblies' length depends on concentration and consists of similar to 23 molecules in the N phase, becoming three to ten times larger in the M phase. The scission energy is concentration dependent in the N phase with values similar to 7.19 +/- 0.14 k(B)T (15 wt%), 2.73 +/- 0.4 k(B)T (20 wt%), and 3.05 +/- 0.2 k(B)T (25 wt%). Solutions of all concentrations undergo a spinodal decomposition at temperatures above similar to 40 degrees C, resulting in DSCG-rich regions with the M phase and water-rich regions in the N and isotropic phases.