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首页> 美国卫生研究院文献>The Journal of Chemical Physics >Counterion adsorption theory of dilute polyelectrolyte solutions: Apparent molecular weight second virial coefficient and intermolecular structure factor
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Counterion adsorption theory of dilute polyelectrolyte solutions: Apparent molecular weight second virial coefficient and intermolecular structure factor

机译：稀聚电解质溶液的抗衡离子吸附理论：表观分子量第二维里系数和分子间结构因子

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摘要

Polyelectrolyte chains are well known to be strongly correlated even in extremely dilute solutions in the absence of additional strong electrolytes. Such correlations result in severe difficulties in interpreting light scattering measurements in the determination of the molecular weight, radius of gyration, and the second virial coefficient of charged macromolecules at lower ionic strengths from added strong electrolytes. By accounting for charge-regularization of the polyelectrolyte by the counterions, we present a theory of the apparent molecular weight, second virial coefficient, and the intermolecular structure factor in dilute polyelectrolyte solutions in terms of concentrations of the polymer and the added strong electrolyte. The counterion adsorption of the polyelectrolyte chains to differing levels at different concentrations of the strong electrolyte can lead to even an order of magnitude discrepancy in the molecular weight inferred from light scattering measurements. Based on counterion-mediated charge regularization, the second virial coefficient of the polyelectrolyte and the interchain structure factor are derived self-consistently. The effect of the interchain correlations, dominating at lower salt concentrations, on the inference of the radius of gyration and on molecular weight is derived. Conditions for the onset of nonmonotonic scattering wave vector dependence of scattered intensity upon lowering the electrolyte concentration and interpretation of the apparent radius of gyration are derived in terms of the counterion adsorption mechanism.
机译：众所周知，即使在没有其他强电解质的情况下，在极稀溶液中，聚电解质链也具有很强的相关性。这种相关性在确定分子量，回转半径和在较低离子强度下由添加的强电解质产生的带电大分子的第二维里系数时，难以解释光散射测量结果。通过考虑抗衡离子对聚电解质的电荷调节作用，我们提出了一种基于聚合物和添加的强电解质浓度的稀聚电解质溶液中表观分子量，第二维里系数和分子间结构因子的理论。在强电解质的不同浓度下，聚电解质链的抗衡离子吸附达到不同的水平，可能导致从光散射测量得出的分子量甚至出现一个数量级的差异。基于抗衡离子介导的电荷正则化，可自洽地得出聚电解质的第二病毒系数和链间结构因子。得出了在较低盐浓度下占支配地位的链间相关性对回转半径和分子量的影响。从抗衡离子吸附机理出发，推导了散射强度随电解质浓度的降低而发生非单调散射波矢量依赖性的条件，以及对表观回转半径的解释。

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