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Combined depletion and electrostatic forces in polymer-induced membrane adhesion: A theoretical model

机译:聚合物诱导的膜粘附中的耗竭和静电力结合:理论模型

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We develop a semi-quantitative analytical theory to describe adhesion between two identical planar charged surfaces embedded in a polymer-containing electrolyte solution. Polymer chains are uncharged and differ from the solvent by their lower dielectric permittivity. The solution mimics physiological fluids: It contains 0.1 M of monovalent ions and a small number of divalent cations that form tight bonds with the headgroups of charged lipids. The components have heterogeneous spatial distributions. The model was derived self-consistently by combining: (a) a Poisson-Boltzmann like equation for the charge densities, (b) a continuum mean-field theory for the polymer profile, (c) a solvation energy forcing the ions toward the polymer-poor regions, and (d) surface interactions of polymers and electrolytes. We validated the theory via extensive coarse-grained Molecular Dynamics (MD) simulations. The results confirm our analytical model and reveal interesting details not detected by the theory. At high surface charges, polymer chains are mainly excluded from the gap region, while the concentration of ions increases. The model shows a strong coupling between osmotic forces, surface potential and salting-out effects of the slightly polar polymer chains. It highlights some of the key differences in the behaviour of monomeric and polymeric mixed solvents and their responses to Coulomb interactions. Our main findings are: (a) the onset of long-ranged ion-induced polymer depletion force that increases with surface charge density and (b) a polymer-modified repulsive Coulomb force that increases with surface charge density. Overall, the system exhibits homeostatic behaviour, resulting in robustness against variations in the amount of charges. Applications and extensions of the model are briefly discussed.
机译:我们开发了一种半定量分析理论来描述嵌入含聚合物的电解质溶液中的两个相同的平面带电表面之间的粘附力。聚合物链不带电荷,并且由于其较低的介电常数而与溶剂不同。该溶液模拟生理流体:它包含0.1 M单价离子和少量二价阳离子,它们与带电脂质的头基形成紧密键。组件具有异构的空间分布。该模型是通过以下方式自洽地得出的:(a)电荷密度的Poisson-Boltzmann式方程;(b)聚合物分布的连续平均场理论;(c)迫使离子朝向聚合物的溶剂化能-不良区域,以及(d)聚合物和电解质的表面相互作用。我们通过广泛的粗粒度分子动力学(MD)模拟验证了该理论。结果证实了我们的分析模型,并揭示了该理论未发现的有趣细节。在高表面电荷的情况下,聚合物链主要从间隙区域排除,而离子浓度增加。该模型显示了渗透力,表面电位和微极性聚合物链的盐析效应之间的强耦合。它着重说明了单体和聚合物混合溶剂的行为及其对库仑相互作用的响应方面的一些关键差异。我们的主要发现是:(a)长距离离子诱导的聚合物耗尽力的出现,其随着表面电荷密度的增加而增加;(b)聚合物改性的排斥库仑力的增加,其随着表面电荷密度的增加而增加。总体而言,该系统表现出稳态性能,从而可抵御电荷量的变化。简要讨论了该模型的应用和扩展。

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