聚电解质
反离子
电介质
水溶液
化学物理
吸附
化学
基质(水族馆)
盐(化学)
静电学
单层
离子
化学工程
材料科学
聚合物
物理化学
有机化学
海洋学
光电子学
工程类
地质学
生物化学
作者
Hossein Vahid,Alberto Scacchi,Maria Sammalkorpi,Tapio Ala-Nissilä
摘要
We examine the interactions between polyelectrolytes (PEs) and uncharged substrates under conditions corresponding to a dielectric discontinuity between the aqueous solution and the substrate. To this end, we vary the relevant system characteristics, in particular the substrate dielectric constant ɛs under different salt conditions. We employ coarse-grained molecular dynamics simulations with rodlike PEs in salt solutions with explicit ions and implicit water solvent with dielectric constant ɛw = 80. As expected, at low salt concentrations, PEs are repelled from the substrates with ɛs < ɛw but are attracted to substrates with a high dielectric constant due to image charges. This attraction considerably weakens for high salt and multivalent counterions due to enhanced screening. Furthermore, for monovalent salt, screening enhances adsorption for weakly charged PEs, but weakens it for strongly charged ones. Meanwhile, multivalent counterions have little effect on weakly charged PEs, but prevent adsorption of highly charged PEs, even at low salt concentrations. We also find that correlation-induced charge inversion of a PE is enhanced close to the low dielectric constant substrates, but suppressed when the dielectric constant is high. To explore the possibility of a PE monolayer formation, we examine the interaction of a pair of like-charged PEs aligned parallel to a high dielectric constant substrate with ɛs = 8000. Our main conclusion is that monolayer formation is possible only for weakly charged PEs at high salt concentrations of both monovalent and multivalent counterions. Finally, we also consider the energetics of a PE approaching the substrate perpendicular to it, in analogy to polymer translocation. Our results highlight the complex interplay between electrostatic and steric interactions and contribute to a deeper understanding of PE–substrate interactions and adsorption at substrate interfaces with varying dielectric discontinuities from solution, ubiquitous in biointerfaces, PE coating applications, and designing adsorption setups.
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