Physical Chemistry and Soft Matter, Wageningen University and Research , Stippeneng 4, 6708 WE Wageningen, The Netherlands.
L'Oréal Research and Innovation , 1 Av. Eugene Scheuller, 93600 Aulnay sous Bois, France.
J Phys Chem B. 2017 Sep 21;121(37):8638-8651. doi: 10.1021/acs.jpcb.7b05195. Epub 2017 Sep 12.
Depositing cationic polyelectrolytes (PEs) from micellar solutions that include surfactants (SU) onto surfaces is a rich, complex, highly relevant, and challenging topic that covers a broad field of practical applications (e.g., from industrial to personal care). The role of the molecular architecture of the constituents of the PEs are often overruled, or at least and either, underestimated in regard to the surface properties. In this work, we aim to evaluate the effect of a model biomimetic surface that shares the key characteristics of the extreme surface of hair and its concomitant chemo- and physisorbed properties onto the deposition of a complex PEs:SU system. To tackle out the effect of the molecular architecture of the PEs, we consider (i) a purely linear and hydrophilic PE (P) and (ii) a PE with lateral amphiphilic chains (PegPE). Using numerical self-consistent field calculations, we show that the architecture of the constituents interfere with the surface properties in a nonintuitive way such that, depending on the amphiphilicity and hydrophilicity of the PEs and the hydrophobicity of the surface, a re-entrant adsorbing transition can be observed, the lipid coverage of the model hair surface being the unique control parameter. Such a behavior is rationalized by the anticooperative associative properties of the coacervate micelles in solution, which is also controlled by the architecture of the PEs and SU. We now expect that PEs adsorption, as a rule, is governed by the molecular details of the species in solution as well as the surface specificities. We emphasize that molecular realistic modeling is essential to rationalize and optimize the adsorption process of, for example, polymer conditioning agents in water-rinsed cosmetic or textile applications.
从包含表面活性剂 (SU) 的胶束溶液中沉积阳离子聚电解质 (PE) 到表面是一个丰富、复杂、高度相关且具有挑战性的话题，涵盖了广泛的实际应用领域（例如，从工业到个人护理）。PE 组成部分的分子结构的作用通常被忽视，或者至少被低估，而在表面性质方面则被忽视。在这项工作中，我们旨在评估具有毛发极端表面关键特征的模型仿生表面以及随之而来的化学和物理吸附特性对复杂 PE:SU 系统沉积的影响。为了研究 PE 的分子结构对沉积的影响，我们考虑了 (i) 纯线性和亲水 PE (P) 和 (ii) 具有侧链两亲性的 PE (PegPE)。使用数值自洽场计算，我们表明，组成部分的结构以一种非直观的方式干扰表面性质，使得取决于 PE 和表面疏水性的亲水性和两亲性，可以观察到重新进入吸附转变，模型毛发表面的脂质覆盖率是唯一的控制参数。这种行为可以通过共凝聚胶束在溶液中的反协作缔合性质来合理化，这也受到 PE 和 SU 的结构控制。我们现在预计，PE 的吸附通常受溶液中物种的分子细节以及表面特异性的控制。我们强调，分子现实建模对于合理化和优化例如在水冲洗化妆品或纺织应用中的聚合物调理剂的吸附过程是至关重要的。
