AI 中文总结
该研究通过匹配平动扩散系数分离旋转扩散的影响，发现大分子结合概率依赖内部结构，自组装路径受旋转扩散系数影响，建立了大分子平衡动力学与自组装动力学的关联。
AI 中文摘要
大分子自组装是众多生物过程的基础，也为制备功能性软材料提供了通用途径。溶液中自组装的动力学本质上是随机的，根本上由构成大分子的平动扩散与旋转扩散的相互作用所支配。多数计算研究将大分子建模为带斑块的球形胶体，忽略了聚合物结构与内部构象动力学的影响，而这些因素在大分子自组装动力学中的作用仍知之甚少。本研究考察两种不同结构的带斑块大分子的自组装，即线性链以及具有四个和七个臂的星形聚合物。所选大分子的流体力学半径近乎相同，以此匹配它们的平动扩散系数，从而分离出旋转扩散对自组装过程的影响。研究发现，带斑块大分子的结合概率强烈依赖于其内部结构；此外，反应路径密度分析表明，自组装路径受单个大分子的旋转扩散系数影响。总体而言，本研究在大分子的平衡动力学与其自组装动力学之间建立了桥梁，凸显了聚合物内部结构在自组装过程中的重要性。
英文摘要
Macromolecular self-assembly underlies a plethora of biological processes and provides a versatile route for fabricating functional soft materials. The kinetics of self-assembly in solution are inherently stochastic and are fundamentally governed by the interplay of translational and rotational diffusion of the constituent macromolecules. While most computational studies model macromolecules as patchy spherical colloids, thereby neglecting the influence of polymer architecture and internal conformational dynamics, the role of these factors in macromolecular self-assembly kinetics remains poorly understood. Here, we investigate the self-assembly of two patchy macromolecules with different architectures, namely linear chains and star polymers with four and seven arms. The hydrodynamic radii of the macromolecules are chosen to be nearly identical, thereby matching their translational diffusion coefficients and thus isolating the influence of rotational diffusion on the self-assembly process. The binding probability of the patchy macromolecules is found to depend strongly on their internal architecture. Furthermore, reactive path density analysis reveals that self-assembly pathways are influenced by the rotational diffusion coefficient of the individual macromolecules. Overall, this study establishes a bridge between the equilibrium dynamics of macromolecules and their self-assembly kinetics, highlighting the importance of polymer internal architecture in the process of self-assembly.
Comments26 pages, 8 figures
