Light-Triggered Rheological Changes in a System of Cationic Wormlike Micelles Formulated with a Photoacid Generator.

"Smart" fluids displaying large changes in their rheological properties in response to external stimuli have been of great interest in recent years. For example, "smart" wormlike micelles (WLMs) that respond to pH can be readily formulated by combining a cationic surfactant such as cetyltrimethylammonium bromide (CTAB) with an aromatic compound such as 1,2-dihydroxybenzene (DHB). Here, we show that a pH-responsive aqueous formulation as mentioned above can be simultaneously made responsive to ultraviolet (UV) light by incorporating a photoacid generator (PAG) into the system. A commercially available PAG, diphenyliodonium-2-carboxylate, is used here. Upon exposure to UV light, this PAG irreversibly photolyzes into iodobenzene (IB) and benzoic acid (BA), with the formation of BA, leading to a drop in pH. WLMs formed by mixtures of CTAB, DHB, and the PAG are systematically characterized before and after UV irradiation. As the PAG photolyzes, an increase in the viscosity of WLMs occurs by a factor of 1000. We show that the ratio of the zero-shear viscosity η0 (after UV/before UV) depends on the initial pH of the sample. The UV-induced increase in η0 can be attributed to the growth of WLMs in solution, which in turn is influenced by both the ionization state of DHB and the presence of IB and BA.

A new interpretation of the mechanism of wormlike micelle formation involving a cationic surfactant and salicylate.

HYPOTHESIS: When tetradecyltrimethylammonium bromide, TTAB, is added to aqueous solution of sodium salicylate, NaSal, the threading of the aromatic anion into the micellar palisade leads to the formation of wormlike micelles. Based on the calorimetric titration of NaSal with TTAB, and on the lifetime of fluorescence of salicylate, we propose that the aggregation of the two components directly leads to the formation of wormlike micelles, without any pre-aggregation. EXPERIMENTS: By using an isothermal titration calorimeter, aliquots of TTAB were added to a dilute solution of NaSal. The energy involved in each addition was then integrated and the variation of enthalpy was determined. In the same range of concentrations and molar ratios, the surface tensiometry and time-resolved emission spectroscopy experiments were performed. FINDINGS: A very characteristic calorimetric signal associated with wormlike micelle formation was obtained, being the enthalpy variation of this process, ΔWLMH2980 < 0. When 1.2 mmol L-1 of NaSal is titrated with 11.0 mmol L-1 of TTAB at 298.15 K, ΔfH2980 = -10.31 kJ per mol of injectant. By adding TTAB to NaSal solution, two fluorescence lifetimes of salicylate were observed solely after wormlike micelle being formed. The correspondent lifetime values of 4.0 ns and 7.2 ns are respectively associated with the free and associated species of salicylate. The new results demonstrated that wormlike micelles are the first aggregate formed when TTAB is added to salicylate. This aspect is relevant for understanding the mechanism of wormlike micelles formation.