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本体中及受平面壁限制的半柔性聚合物。

Semiflexible Polymers in the Bulk and Confined by Planar Walls.

作者信息

Egorov Sergei A, Milchev Andrey, Binder Kurt

机构信息

Department of Chemistry, University of Virginia, Charlottesville, VA 22901, USA.

Institut für Physik, Johannes Gutenberg Universität Mainz, 55099 Mainz, Germany.

出版信息

Polymers (Basel). 2016 Aug 10;8(8):296. doi: 10.3390/polym8080296.

Abstract

Semiflexible polymers in solution under good solvent conditions can undergo an isotropic-nematic transition. This transition is reminiscent of the well-known entropically-driven transition of hard rods described by Onsager's theory, but the flexibility of the macromolecules causes specific differences in behavior, such as anomalous long wavelength fluctuations in the ordered phase, which can be understood by the concept of the deflection length. A brief review of the recent progress in the understanding of these problems is given, summarizing results obtained by large-scale molecular dynamics simulations and density functional theory. These results include also the interaction of semiflexible polymers with hard walls and the wall-induced nematic order, which can give rise to capillary nematization in thin film geometry. Various earlier theoretical approaches to these problems are briefly mentioned, and an outlook on the status of experiments is given. It is argued that in many cases of interest, it is not possible to describe the scaled densities at the isotropic-nematic transition as functions of the ratio of the contour length and the persistence length alone, but the dependence on the ratio of chain diameter and persistence length also needs to be considered.

摘要

在良溶剂条件下,溶液中的半柔性聚合物会经历各向同性向向列相的转变。这种转变让人联想到由昂萨格理论描述的、众所周知的硬棒熵驱动转变,但大分子的柔性导致了行为上的特定差异,比如有序相中异常的长波长涨落,这可以通过偏转长度的概念来理解。本文简要回顾了在理解这些问题方面的最新进展,总结了通过大规模分子动力学模拟和密度泛函理论获得的结果。这些结果还包括半柔性聚合物与硬壁的相互作用以及壁诱导的向列相序,这在薄膜几何结构中会导致毛细向列相化。文中简要提及了处理这些问题的各种早期理论方法,并对实验现状进行了展望。有人认为,在许多相关情况下,仅将各向同性 - 向列相转变时的标度密度描述为轮廓长度与持久长度之比的函数是不可能的,还需要考虑链直径与持久长度之比的依赖性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e0f3/6432127/6715a319820a/polymers-08-00296-g001.jpg

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