*Article* **Computational Investigations of a pH-Induced Structural Transition in a CTAB Solution with Toluic Acid**

**Tingyi Wang <sup>1</sup> , Hui Yan 2,\* , Li Lv <sup>3</sup> , Yingbiao Xu <sup>1</sup> , Lingyu Zhang <sup>1</sup> and Han Jia <sup>4</sup>**


**Abstract:** In this work, molecular dynamics simulations were performed to study the pH-induced structural transitions for a CTAB/*p*-toluic acid solution. Spherical and cylindrical micelles were obtained for aqueous surfactants at pH 2 and 7, respectively, which agrees well with the experimental observations. The structural properties of two different micelles were analyzed through the density distributions of components and the molecular orientations of CTA<sup>+</sup> and toluic acid inside the micelles. It was found that the bonding interactions between CTA<sup>+</sup> and toluic in spherical and cylindrical micelles are very different. Almost all the ionized toluic acid (PTA−) in the solution at pH 7 was solubilized into the micelles, and it was located in the CTA<sup>+</sup> headgroups region. Additionally, the bonding between surfactant CTA<sup>+</sup> and PTA<sup>−</sup> was very tight due to the electrostatic interactions. The PTA− that penetrated into the micelles effectively screened the electrostatic repulsion among the cationic headgroups, which is considered to be crucial for maintaining the cylindrical micellar shape. As the pH decreased, the carboxyl groups were protonated. The hydration ability of neutral carboxyl groups weakened, resulting in deeper penetration into the micelles. Meanwhile, their bonding interactions with surfactant headgroups also weakened. Accompanied by the strengthen of electrostatic repulsion among the positive headgroups, the cylindrical micelle was broken into spherical micelles. Our work provided an atomic-level insights into the mechanism of pH-induced structural transitions of a CTAB/*p*-toluic solution, which is expected to be useful for further understanding the aggregate behavior of mixed cationic surfactants and aromatic acids.

**Keywords:** molecular dynamics simulation; pH-induced structural transitions; rodlike micelle; sphecial micelle; cationic surfactant
