Manning G S
Biophys Chem. 1977 Sep;7(2):95-102. doi: 10.1016/0301-4622(77)80002-1.
The limiting laws for polyelectrolyte solutions developed in previous papers of this series have been amply confirmed by measurement. A surprising result of the accumulated data is that the limiting polyelectrolyte charge fraction (fraction of fixed charges uncompensated by condensed counterions in the limit of zero concentration), persists up to concentrations of 0.1 M or even higher. Here the theory is extended in a simple manner to finite concentrations, and the stability of the charge fraction is found to be firmly based on consequences of the long-range polyelectrolyte field. The associated counterions are assumed to translate freely in a region centered on the contour axis of the polyion. The numerical value of the free volume is determined self-consistently from the axial charge density of the polyelectrolyte and is used as the general framework within which specific binding effects are treated.
本系列前文所推导的聚电解质溶液极限定律已通过测量得到充分证实。累积数据的一个惊人结果是，极限聚电解质电荷分数（在零浓度极限下未被凝聚反离子补偿的固定电荷分数）在浓度高达0.1 M甚至更高时依然存在。在此，该理论以一种简单的方式扩展到有限浓度，并且发现电荷分数的稳定性牢固地基于聚电解质长程场的结果。假定相关反离子在以聚离子轮廓轴为中心的区域内自由移动。自由体积的数值由聚电解质的轴向电荷密度自洽确定，并用作处理特定结合效应的一般框架。
