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通过多孔介质的半刚性聚合物蠕动。

Reptation of a semiflexible polymer through porous media.

机构信息

Department of Physics, Institute of Fundamental Physics, Sejong University, Seoul 143-743, South Korea.

出版信息

J Chem Phys. 2010 Jul 28;133(4):044908. doi: 10.1063/1.3457999.

Abstract

We study the motion of a single stiff semiflexible filament of length S through an array of topological obstacles. By means of scaling arguments and two-dimensional computer simulations, we show that the stiff chain kinetics follows the reptation picture, albeit with kinetic exponents (for the central monomer) different from those for flexible chain reptation. At early times when topological constraints are irrelevant, the chain kinetics is the anisotropic dynamics of a free filament. After the entanglement time tau(e) transverse modes are equilibrated under the topological constraints, but the chain is not yet correlated over its whole length. During the relaxation of longitudinal modes, both the longitudinal fluctuation of the central monomer and the longitudinal correlation length grow as approximately sqrt t. After time tau(r) approximately S(2) chain ends are correlated, the chain then diffuses globally along the tube and tube renewal takes place. In the reptation regime, the longitudinal fluctuation of the central monomer grows like approximately t(1). The opening of the intermediate approximately sqrt t regime, absent for a free filament, is a signature of the reptation process. Although the underlying physics is quite different, the intermediate regime is reminiscent of the internal Rouse mode relaxation found for reptating flexible chains. In most cases asymptotic power laws from scaling could be complemented by prefactors calculated analytically. Our results are supported by two-dimensional Langevin simulations with fixed obstacles via evaluation of the mean squared displacement of the central monomer. The scaling theory can be extended to long semiflexible polymers adopting random-walk equilibrium configurations and should also apply in three dimensions for porous media with pore diameter smaller than the persistence length of the filament.

摘要

我们研究了长度为 S 的单个刚性半柔性长丝在一系列拓扑障碍物中的运动。通过标度分析和二维计算机模拟,我们表明刚性链的动力学遵循蠕动图像,尽管其动力学指数(对于中心单体)与柔性链蠕动的动力学指数不同。在拓扑约束不相关的早期,链动力学是自由长丝的各向异性动力学。在缠结时间 tau(e)之后,横向模式在拓扑约束下达到平衡,但链尚未在其整个长度上相关。在纵向模式的松弛过程中,中心单体的纵向涨落和纵向相关长度都以近似 sqrt t 的方式增长。在时间 tau(r)大约 S(2)链端相关之后,链随后沿管整体扩散,管更新发生。在蠕动状态下,中心单体的纵向涨落增长类似于 approximately t(1)。对于自由长丝不存在的中间 approximately sqrt t 区域的打开是蠕动过程的特征。尽管基础物理完全不同,但中间区域让人想起了蠕动柔性链中发现的内部 Rouse 模式松弛。在大多数情况下,来自标度的渐近幂律可以通过解析计算的前因子来补充。我们的结果得到了通过评估中心单体的均方位移的二维 Langevin 模拟与固定障碍物的支持。该标度理论可以扩展到采用随机行走平衡构型的长半柔性聚合物,并且应该也适用于三维多孔介质,其中孔直径小于长丝的持久长度。

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