Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux, UMR 5254 CNRS UPPA, Pau, France.
Institute of Macromolecular Compounds of the Russian Academy of Sciences, St. Petersburg, Russia.
J Chem Phys. 2017 Jun 7;146(21):214901. doi: 10.1063/1.4984101.
Polyelectrolyte brushes are formed by charged macromolecules tethered by the end segment to a solid-liquid interface. At low ionic strength of the solution, the intermolecular electrostatic interactions lead to strong stretching of the macromolecules that may, as a result, approach the limit of their extensibility (the contour length). Here, we present an analytical theory of polyelectrolyte brushes developed within the Poisson-Boltzmann approximation which explicitly accounts for finite extensibility of the brush-forming chains. In contrast to earlier theories based on the approximation of Gaussian elasticity of the brush-forming chains, the current approach enables avoiding artificial result of stretching of the chains beyond the contour length at high degrees of ionization or/and large grafting densities.
聚电解质刷由通过末端段固定在固-液界面上的带电大分子形成。在溶液的离子强度较低的情况下，分子间的静电相互作用导致大分子强烈拉伸，这可能导致大分子接近其可伸展性的极限（轮廓长度）。在这里，我们提出了一种在泊松-玻尔兹曼近似内发展的聚电解质刷的分析理论，该理论明确考虑了刷形成链的有限可伸展性。与基于刷形成链的高斯弹性近似的早期理论相反，当前方法能够避免在高电离度或/和大接枝密度下，链的拉伸超出轮廓长度的人为结果。
