Sensitivity of cationic surfactant templates to specific anions in liquid interface crystallization

We investigated the specific effects of potassium salts of various anions upon the interfacially templated crystal nucleation of K(2)SO(4). Previously, we have shown that the presence of several salts at low concentrations could induce changes in important crystallization characteristics templated by 1-octadecylamine at the liquid-liquid interface, and that these changes depended greatly on the specific identity of the salt. In this work we extend our surfactant monolayers to include dimethyldioctadecylammonium bromide (DODAB) and hexadecyltrimethylammonium bromide (CTAB). Addition of 10 mM of various potassium salts results in a diminution in efficiency of the templating capability of CTAB monolayer, as evidenced by higher C(onset) values and polycrystalline habit. The ability of the anions to perturb these values varied in a manner consistent with a Hofmeister series. However, DODAB maintained its templating effectiveness regardless of the nature of the salt or concentration. DODAB and CTAB are likely to be undergoing different reordering effects in the monolayer upon binding with chaotropic anions: a combined reduction in surface charge with different monolayer ordering results in a differing template ability. These studies have provided significant insights into the understanding of the interaction of ordered surfactant arrays with salts, and provide exciting possibilities for crystal engineering and materials design.