Description of surfactant 2D monolayer formation at the air/water interface within semiempirical quantum chemistry

Q3 Materials Science
E.S. Kartashynska , D. Vollhardt
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Abstract

The review discusses the development of a quantum chemical approach for calculating the thermodynamic clusterization parameters of surfactants at the air/water interface. It characterizes the intermolecular interactions that govern the process of surfactant association. Of particular interest are the dispersion interactions CH···HC between the hydrophobic chains of surfactants, as well as their accurate description within the exploited scheme and semiempirical methods. The scheme is based on calculating the thermodynamic parameters of formation for a certain number of surfactant monomers and small clusters with different chain lengths using the supermolecule approximation. Furthermore, it enables the construction of an additive scheme with assessed values of the increments of CH···HC interactions and interactions between the hydrophilic parts. This scheme provides equations for thermodynamic clusterization parameters per one surfactant molecule of infinite 2D films. The number of parameters adequately assessed within this approach is described in the previous review in Colloid Polym. Sci., 2015, 293, 3065–3089: the threshold chain length of spontaneous clusterization, the “temperature effect” of clusterization, and the assessment of the molecular tilt angle of the surfactant with respect to the interface. In this context, our aim is to describe additional parameters and experimental phenomena. These include the dependence of the area per surfactant molecule in a 2D monolayer at the LE-LC phase transition on temperature and chain length, the correlation of the surfactant clusterization threshold with the solubility threshold, and with the donor-acceptor properties of the substituents included in the hydrophilic part. We also explore surfactant binary mixtures, surfactant – alkane mixtures, and the role of amphiphiles in the formation of alkane adsorption layers. Additionally, we investigate the shifting of the acid or base value (pKa, pKb) of surfactants with chain elongation during monolayer formation, as well as the dendricity of surfactant domains with an increase in temperature or shortening of chain length.

Abstract Image

在半经验量子化学中描述空气/水界面上表面活性剂二维单层的形成
综述讨论了计算空气/水界面表面活性剂热力学聚类参数的量子化学方法的发展。它描述了支配表面活性剂结合过程的分子间相互作用。特别值得关注的是表面活性剂疏水链之间的分散相互作用 CH----HC,以及在所利用的方案和半经验方法中对它们的精确描述。该方案的基础是利用超分子近似法计算一定数量的表面活性剂单体和不同链长的小簇的形成热力学参数。此外,该方法还可以构建一个加法方案,对 CH--HC 相互作用和亲水部分之间相互作用的增量进行评估。该方案提供了无限二维薄膜中每个表面活性剂分子的热力学聚类参数方程。在《Colloid Polym.Sci.,2015,293,3065-3089 中的综述中描述了:自发聚类的阈值链长、聚类的 "温度效应 "以及表面活性剂相对于界面的分子倾斜角评估。在此背景下,我们的目标是描述更多参数和实验现象。其中包括在 LE-LC 相变时二维单层中每个表面活性剂分子的面积对温度和链长的依赖性、表面活性剂聚类阈值与溶解度阈值的相关性,以及与亲水部分所含取代基的供体-受体特性的相关性。我们还探讨了表面活性剂二元混合物、表面活性剂-烷烃混合物以及两性化合物在形成烷烃吸附层中的作用。此外,我们还研究了在单层形成过程中,表面活性剂的酸值或碱值(pKa、pKb)会随着链的拉长而发生变化,以及表面活性剂畴的树枝性会随着温度的升高或链长度的缩短而发生变化。
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来源期刊
JCIS open
JCIS open Physical and Theoretical Chemistry, Colloid and Surface Chemistry, Surfaces, Coatings and Films
CiteScore
4.10
自引率
0.00%
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0
审稿时长
36 days
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