Rauscher Phillip M, de Pablo Juan J
Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States.
Materials Science Division (MSD) and Center for Molecular Engineering (CME), Argonne National Laboratory, Lemont, Illinois 60439, United States.
Macromolecules. 2022 Sep 27;55(18):8409-8417. doi: 10.1021/acs.macromol.2c01676. Epub 2022 Sep 8.
Many ring polymer systems of physical and biological interest exhibit both pronounced topological effects and nontrivial self-similarity, but the relationship between these two phenomena has not yet been clearly established. Here, we use theory and simulation to formulate such a connection by studying a fundamental topological property-the random knotting probability-for ring polymers with varying fractal dimension, . Using straightforward scaling arguments, we generalize a classic mathematical result, showing that the probability of a trivial knot decays exponentially with chain size, , for all fractal dimensions: () ∝ exp(-/ ). However, no such simple considerations can account for the dependence of the knotting length, , on , necessitating a more involved analytical calculation. This analysis reveals a complicated double-exponential dependence, which is well supported by numerical data. By contrast, functional forms typical of simple scaling theories fail to adequately describe the observations. These findings are equally valid for two-dimensional ring polymer systems, where "knotting" is defined as the intersection of any two segments.
许多具有物理和生物学意义的环状聚合物系统既表现出明显的拓扑效应,又具有非平凡的自相似性,但这两种现象之间的关系尚未明确确立。在此,我们通过研究具有不同分形维数(D)的环状聚合物的一种基本拓扑性质——随机打结概率,利用理论和模拟来建立这样一种联系。通过直接的标度论证,我们推广了一个经典数学结果,表明对于所有分形维数,平凡结的概率随链尺寸(N)呈指数衰减:(P(N) \propto \exp(-N / N_0))。然而,没有这样简单的考虑能够解释打结长度(N_k)对(D)的依赖性,这就需要进行更复杂的解析计算。该分析揭示了一种复杂的双指数依赖性,这得到了数值数据的有力支持。相比之下,简单标度理论的典型函数形式无法充分描述这些观测结果。这些发现对于二维环状聚合物系统同样有效,在二维系统中,“打结”被定义为任意两条链段的相交。