Department of Polymer Science and Engineering, University of Massachusetts, Amherst, Massachusetts 01003, USA.
J Chem Phys. 2017 Jun 28;146(24):244901. doi: 10.1063/1.4986961.
We present a theory of adsorption of flexible polyelectrolytes on the interior and exterior surfaces of a charged vesicle in an electrolyte solution. The criteria for adsorption and the density profiles of the adsorbed polymer chain are derived in terms of various characteristics of the polymer, vesicle, and medium, such as the charge density and length of the polymer, charge density and size of the vesicle, electrolyte concentration and dielectric constant of the medium. For adsorption inside the vesicle, the competition between the loss of conformational entropy and gain in adsorption energy results in two kinds of encapsulated states, depending on the strength of the polymer-vesicle interaction. By considering also the adsorption from outside the vesicle, we derive the entropic and energy contributions to the free energy change to transfer an adsorbed chain in the interior to an adsorbed chain on the exterior. In this paper, we have used the Wentzel-Kramers-Brillouin (WKB) method to solve the equation for the probability distribution function of the chain. The present WKB results are compared with the previous results based on variational methods. The WKB and variational results are in good agreement for both the interior and exterior states of adsorption, except in the zero-salt limit for adsorption in the exterior region. The adsorption criteria and density profiles for both the interior and exterior states are presented in terms of various experimentally controllable variables. Calculation of the dependencies of free energy change to transfer an adsorbed chain from the interior to the exterior surface on salt concentration and vesicle radius shows that the free energy penalty to expel a chain from a vesicle is only of the order of thermal energy.
我们提出了一种在电解质溶液中带电荷囊泡的内外表面上柔性聚合物电解质吸附的理论。吸附的标准和吸附聚合物链的密度分布是根据聚合物、囊泡和介质的各种特性得出的,例如聚合物的电荷密度和长度、囊泡的电荷密度和大小、电解质浓度和介质的介电常数。对于在囊泡内部的吸附,构象熵的损失和吸附能的增加之间的竞争导致了两种封装状态,这取决于聚合物-囊泡相互作用的强度。通过考虑从囊泡外部的吸附,我们推导出了将内部吸附链转移到外部吸附链的自由能变化的熵和能量贡献。在本文中,我们使用了 Wentzel-Kramers-Brillouin(WKB)方法来求解链的概率分布函数方程。将目前的 WKB 结果与基于变分方法的先前结果进行了比较,除了在外部区域吸附的零盐极限外,WKB 和变分结果对于吸附的内部和外部状态都非常吻合。吸附的标准和吸附的内部和外部状态的密度分布都是根据各种可实验控制的变量来表示的。计算从内部到外部表面转移吸附链的自由能变化对盐浓度和囊泡半径的依赖性表明,从囊泡中排出链的自由能罚仅为热能的量级。