Hybrid Field Theory and Particle Simulation Model of Polyelectrolyte–Surfactant Coacervation
Hybrid Field Theory and Particle Simulation Model of Polyelectrolyte–Surfactant Coacervation
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聚电解质-表面活性剂凝聚的混合场理论与粒子模拟模型
DOI：
10.1021/acs.macromol.2c00187
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发表时间：
2022
期刊：
影响因子：
5.5
通讯作者：
Sing, Charles E.
中科院分区：
文献类型：
--
作者：
Madinya, Jason J.;Sing, Charles E.
带相反电荷的聚电解质和表面活性剂的溶液已被广泛研究用于各种应用；它们在个人护理产品的配方中发挥着重要作用，可以作为药物包封的有效策略，并且可以作为生物分子凝聚物等生物系统的类似物。表面活性剂分子自组装成胶束大离子，已知与带相反电荷的聚电解质形成络合物，并且可以经历称为复杂凝聚的大量液-液相分离。这一过程产生了富含宏离子的“凝聚”相和被宏离子稀释的“上清”相。由于这些混合宏观离子体系的不同长度尺度和强库仑相互作用，对这种相分离过程进行建模是具有挑战性的。在这项工作中，我们提出了一个混合模拟和场理论模型来描述聚电解质/表面活性剂溶液，其中表面活性剂物种自组装成蠕虫状胶束结构。我们使用自洽场理论（SCFT）来模拟溶液中与表面活性剂胶束相互作用的聚电解质。表面活性剂胶束结构是通过进行蒙特卡罗（MC）模拟来确定的，该模拟用于确定模型中SCFT部分的外加场。我们使用这些计算来确定聚电解质-表面活性剂凝聚体的系统自由能和相图，并随后考虑一些分子参数的影响，如聚电解质链长度、相互作用胶束表面位点的体积以及聚电解质和胶束表面之间的静电结合能。我们的模型表明，局部电荷-电荷相关是发生相分离的关键。此外，我们还评估了聚电解质胶束桥接的统计数据以及桥接与大离子和盐离子密度之间的关系。该混合SCFT/MC模型可推广到研究各种混合宏离子体系，并对相行为和分子结构进行预测。
Solutions of oppositely charged polyelectrolytes and surfactants have been widely studied for a variety of applications; they play an important role in the formulation of personal care products, can be used as an effective strategy for drug encapsulation, and serve as analogues to biological systems such as biomolecular condensates. Surfactant molecules self-assemble into micellar macroions that are known to form complexes with oppositely charged polyelectrolytes and can undergo a bulk liquid–liquid phase separation known as complex coacervation. This process results in a “coacervate” phase that is rich in macroions and a “supernatant” phase that is dilute in macroions. It is challenging to model this phase separation process due to the disparate length scales and strong Coulombic interactions in these mixed macroion systems. In this work, we present a hybrid simulation and field theory model to describe polyelectrolyte/surfactant solutions, where the surfactant species has self-assembled into worm-like micelle structures. We use self-consistent field theory (SCFT) to model the polyelectrolytes in the solution which interact with the surfactant micelles. The surfactant micelle structures are determined by performing Monte Carlo (MC) simulations, which are used to determine applied external fields in the SCFT portion of the model. We use these calculations to determine the system free energy and map the phase diagrams for polyelectrolyte–surfactant coacervates and subsequently consider the effect of a number of molecular parameters such as polyelectrolyte chain length, the volume of the interacting micelle surface sites, and the electrostatic binding energy between the polyelectrolyte and micelle surface. Our model shows that local charge–charge correlations are critical for phase separation to occur. Additionally, we evaluate the statistics of micelle bridging by the polyelectrolyte and the relationship between bridging and the densities of the macroions and salt ions. This hybrid SCFT/MC model can be generalized to study a variety of mixed macroion systems and make predictions for phase behavior and molecular structure.
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