Predicting Polyelectrolyte Coacervation from a Molecularly Informed Field-Theoretic Model
Predicting Polyelectrolyte Coacervation from a Molecularly Informed Field-Theoretic Model
复制标题
从分子信息场论模型预测聚电解质凝聚
DOI：
10.1021/acs.macromol.2c01759
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发表时间：
2022
期刊：
影响因子：
5.5
通讯作者：
Shell, M. Scott
中科院分区：
文献类型：
--
作者：
Nguyen, My;Sherck, Nicholas;Shen, Kevin;Edwards, Chelsea E.;Yoo, Brian;Köhler, Stephan;Speros, Joshua C.;Helgeson, Matthew E.;Delaney, Kris T.;Shell, M. Scott
了解聚电解质凝聚的相行为对许多应用至关重要，包括消费者配方、湿粘合剂、加工食品和药物输送。然而，在大多数情况下，由于静电力的长程性质和所涉及物种的典型高分子量，通过分子模拟方法不容易获得建模共守。我们提出了一种利用粒子模拟和聚合物场理论的优势来研究复杂凝聚的建模策略。场论特别适合于捕捉粒子模拟无法达到的大长度尺度，但它的预测能力受到指定紧急参数的需要的限制。利用由聚丙烯酸和聚丙烯胺盐酸盐组成的模型凝聚形成系统，我们展示了一种新颖的方法，通过相对熵粗粒化方法，使用小尺度、全原子模拟来参数化场理论模型。在没有拟合实验数据的情况下，预测了聚守恒对盐浓度、分子量和电荷化学计量的依赖，并且与实验趋势一致，包括非化学计量的聚电解质混合物的不对称相行为。这证明了一种独特的模拟方法来研究凝聚形成系统中的相行为，这在化学特异性感兴趣时特别有用。
Understanding the phase behavior of polyelectrolyte coacervation is crucial for many applications, including consumer formulations, wet adhesives, processed food, and drug delivery. However, in most cases, modeling coacervation is not easily accessed by molecular simulation methods due to the long-range nature of electrostatic forces and the typically high molecular weights of the species involved. We present a modeling strategy to study complex coacervation leveraging the strengths of both particle simulations and polymer field theory. Field theory is uniquely suited to capture larger-length scales that are inaccessible to particle simulations, but its predictive capability is limited by the need to specify emergent parameters. Using model coacervate-forming systems consisting of poly(acrylic acid) and poly(allylamine hydrochloride), we show an original way to use small-scale, all-atom simulations to parameterize field-theoretic models via the relative entropy coarse-graining approach. The dependence of coacervation on the salt concentration, molecular weight, and charge stoichiometry is predicted without fitting to experimental data and is consistent with experimental trends including asymmetric phase behavior from non-stoichiometric mixtures of polyelectrolytes. This demonstrates a unique simulation approach to study phase behavior in coacervate-forming systems, which is particularly useful when chemical specificity is of interest.
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DOI：
10.1073/pnas.2201804119
发表时间：
2022-05-03
影响因子：
11.1
作者：
通讯作者：
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影响因子：
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影响因子：
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作者：
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影响因子：
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