Interactions Between Cationic Micellar Solution and Aromatic Hydrotropes with Subtle Structural Variations

Wormlike micelles (WLMs) with tunable viscoelastic characteristics have emerged as indispensable smart materials with a wide range of applications, which have garnered intense interest over the past few decades. However, quantitatively predicting the effect of various hydrotropes on the rheological behaviors of WLMs remains a challenge. In this article, micelles were formed in a mixture of 3-hexadecyloxy-2-hydroxypropyltrimethylammonium bromide (R₁₆HTAB) and aromatic hydrotropes (e.g., sodium benzoate, sodium cinnamate and their derivatives, respectively) in an aqueous solution. The phase behavior, viscoelasticity and thickening mechanism were systematically studied by macroscopic observation, rheological measurements, electrostatic potential analysis and cryogenic transmission electron microscopy (Cryo-TEM). Rheological measurements were used to probe the remarkable viscoelastic properties of micelles stemming from their lengthening and entanglement under the interaction between R₁₆HTAB and hydrotropes with structural variations. For an equimolar system of R₁₆HTAB and cosolute (40 mM), the relaxation time decreases in the following order: SpMB > SoHB > S4MS > SmMB > S5MS > SB > SmHB > SoMB > SpHB. These results allow us to predict the possible rules for the self-assembly of R₁₆HTAB and aromatic hydrotropes, which is conductive to directionally designing and synthesizing smart wormlike micelles.