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Origin of the Sphere-to-Rod Transition in Cationic Micelles with Aromatic Counterions:  Specific Ion Hydration in the Interfacial Region Matters

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posted on 18.01.2005, 00:00 by Yan Geng, Laurence S. Romsted, Sandro Froehner, Dino Zanette, Linda J. Magid, Iolanda M. Cuccovia, Hernan Chaimovich
Sphere-to-rod transitions of cetyltrimethylammonium (CTA+) micelles with dichlorobenzoate counterions are remarkably substituent dependent. Simultaneous estimates of the interfacial molarities of H2O, MeOH, and Cl- and 2,6- and 3,5-dichlorobenzoate (2,6OBz and 3,5OBz) counterions were obtained by the chemical trapping method in mixed micelles of CTACl/CTA3,5OBz and CTACl/CTA2,6OBz without added salt. Increasing the CTA3,5OBz mole fraction produces a marked concurrent increase in interfacial 3,5OBz- and a decrease in interfacial H2O concentrations through the sphere-to-rod transition. No abrupt concentration changes are observed with increasing CTA2,6OBz mole fraction. Counterion-specific changes in the interfacial water concentration may be a major contributor to the delicate balance of forces governing micellar morphology.

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