Manning G S, Ray J
Department of Chemistry, Rutgers University, Piscataway, NJ 08854-8087, USA.
J Biomol Struct Dyn. 1998 Oct;16(2):461-76. doi: 10.1080/07391102.1998.10508261.
We review some of the characteristic properties of the structure of polyelectrolyte solutions: the condensed layer of counterions that forms abruptly at a critical threshold charge density on the polymer chain; the more diffuse Debye-Hückel cloud, which is spatially distinct from the condensed layer; and the entropic release of counterions from the condensed layer as a driving force for the binding of oppositely charged ligands. We present a reminder of the basis of our current understanding in a variety of experiments, simulations, and theories; and we attempt as well to clarify some misunderstandings. We present a new analysis of a lattice model that suggests why the limiting laws for polyelectrolyte thermodynamics have proved to be accurate despite the neglect of polymer-polymer interactions in their original derivation. We sketch recent progress in constructing a potential between counterion and polyion. A counterion located in the interface between condensed layer and Debye cloud is repelled from the polyion, creating a sharp boundary between the two counterion populations.
在聚合物链上的临界阈值电荷密度处突然形成的抗衡离子凝聚层；与凝聚层在空间上不同的更弥散的德拜 - 休克尔云；以及抗衡离子从凝聚层的熵释放作为带相反电荷配体结合的驱动力。我们提醒大家当前在各种实验、模拟和理论方面理解的基础；并且我们也试图澄清一些误解。我们对晶格模型进行了新的分析，这表明尽管在最初推导聚电解质热力学的极限定律时忽略了聚合物 - 聚合物相互作用，但这些定律为何被证明是准确的。我们概述了在构建抗衡离子与聚离子之间势能方面的最新进展。位于凝聚层和德拜云界面的抗衡离子被聚离子排斥，在两种抗衡离子群体之间形成了一个清晰的边界。
