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由半柔性聚合物介导的排空相互作用。

Depletion interaction mediated by semiflexible polymers.

作者信息

Martens C M, Tuinier R, Vis M

机构信息

Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.

出版信息

J Chem Phys. 2022 Oct 21;157(15):154102. doi: 10.1063/5.0112015.

Abstract

We present a simple mean-field theory to describe the polymer-mediated depletion attraction between colloidal particles that accounts for the polymer's chain stiffness. We find that for fixed polymer radius of gyration and volume fraction, the strength of this attraction increases with increasing chain stiffness in both dilute and semidilute concentration regimes. In contrast, the range of attraction monotonically decreases with chain stiffness in the dilute regime, while it attains a maximum in the semidilute regime. The obtained analytical expressions for the depletion interaction were compared with numerical self-consistent field lattice computations and shown to be in quantitative agreement. From the interaction potential between two spheres, we calculated the second osmotic virial coefficient B, which appears to be a convex function of chain stiffness. A minimum of B as a function of chain stiffness was observed both in the numerical self-consistent field computations and the analytical theory. These findings help explain the general observation that semiflexible polymers are more effective depletants than flexible polymers and give insight into the phase behavior of mixtures containing spherical colloids and semiflexible polymers.

摘要

我们提出了一种简单的平均场理论来描述聚合物介导的胶体颗粒间的耗尽吸引作用,该理论考虑了聚合物的链刚性。我们发现,对于固定的聚合物回转半径和体积分数,在稀溶液和半稀溶液浓度范围内,这种吸引力的强度都随着链刚性的增加而增强。相比之下,在稀溶液中,吸引力的范围随链刚性单调减小,而在半稀溶液中则达到最大值。将得到的耗尽相互作用的解析表达式与数值自洽场晶格计算结果进行了比较,结果表明二者在定量上是一致的。根据两个球体之间的相互作用势,我们计算了第二维里系数B,它似乎是链刚性的凸函数。在数值自洽场计算和解析理论中均观察到B作为链刚性的函数存在一个最小值。这些发现有助于解释半柔性聚合物比柔性聚合物更有效的耗尽剂这一普遍观察结果,并深入了解含有球形胶体和半柔性聚合物的混合物的相行为。

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