Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Química Inorgánica Analítica y Química Física, Buenos Aires, Argentina; CONICET - Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Instituto de Química de los Materiales, Ambiente y Energía (INQUIMAE), Buenos Aires, Argentina.
Department of Pharmaceutical Sciences, College of Pharmacy, University of Nebraska Medical Center, Omaha, NE 68198-6125, USA.
J Colloid Interface Sci. 2021 Dec 15;604:757-766. doi: 10.1016/j.jcis.2021.07.001. Epub 2021 Jul 6.
The previously observed effects of nonpolar additives on the scission energy and rheological properties of surfactant wormlike micelles can be explained in terms of the spatial distribution of the additive within the micelles. The dependence of the scission energy with the molecular organization of the system can be analyzed with a molecular theory capable of describing the thermodynamics and structure of the micelles.
A new theoretical method to determine the scission energy of surfactant wormlike micelles is introduced. This methodology is based on a molecular theory that explicitly considers molecular details of all components of the micelles, and their inter- and intramolecular interactions without the use of fitting and/or empirical macroscopic parameters.
The predicted effects of the concentration, molecular structure and hydrophobicity of the additive on the scission energy of cetyltrimethylammonium bromide (CTAB) wormlike micelles are found to be in qualitative agreement with previous experimental observations. In particular, our theory captures the decrease of micellar length with increasing content of highly hydrophobic additives and the non-monotonic dependence of the viscosity with additive hydrophobicity. The latter effect arises because highly and mildly hydrophobic additives affect the scission energy of wormlike micelles via markedly different molecular mechanisms.
先前观察到的非极性添加剂对表面活性剂蠕虫状胶束的断裂能和流变性质的影响,可以用添加剂在胶束内的空间分布来解释。可以用一种能够描述胶束热力学和结构的分子理论来分析断裂能与系统分子组织的关系。
引入了一种新的理论方法来确定表面活性剂蠕虫状胶束的断裂能。该方法基于一种分子理论,该理论明确考虑了胶束中所有成分的分子细节及其分子间和分子内相互作用,而无需使用拟合和/或经验宏观参数。
发现添加剂的浓度、分子结构和疏水性对十六烷基三甲基溴化铵(CTAB)蠕虫状胶束断裂能的预测影响与先前的实验观察结果定性一致。特别是,我们的理论捕捉到了随着高疏水性添加剂含量的增加而导致胶束长度减小,以及随着添加剂疏水性的增加而导致粘度呈非单调变化的现象。后一种效应是因为高度和轻度疏水性添加剂通过明显不同的分子机制影响蠕虫状胶束的断裂能。