Department of Applied Science and Technology, Politecnico di Torino, 10129, Torino, Italy.
Department of Innovative Technologies, University of Applied Sciences and Arts of Southern Switzerland, Polo Universitario Lugano, 6962, Lugano-Viganello, Switzerland.
Nat Commun. 2022 Apr 20;13(1):2162. doi: 10.1038/s41467-022-29804-5.
Supramolecular polymers are composed of monomers that self-assemble non-covalently, generating distributions of monodimensional fibres in continuous communication with each other and with the surrounding solution. Fibres, exchanging molecular species, and external environment constitute a sole complex system, which intrinsic dynamics is hard to elucidate. Here we report coarse-grained molecular simulations that allow studying supramolecular polymers at the thermodynamic equilibrium, explicitly showing the complex nature of these systems, which are composed of exquisitely dynamic molecular entities. Detailed studies of molecular exchange provide insights into key factors controlling how assemblies communicate with each other, defining the equilibrium dynamics of the system. Using minimalistic and finer chemically relevant molecular models, we observe that a rich concerted complexity is intrinsic in such self-assembling systems. This offers a new dynamic and probabilistic (rather than structural) picture of supramolecular polymer systems, where the travelling molecular species continuously shape the assemblies that statistically emerge at the equilibrium.
超分子聚合物由单体自组装而成，这些单体通过非共价键相互作用形成一维纤维的分布，这些纤维与周围的溶液相互连通。纤维、交换的分子物种和外部环境构成了一个单一的复杂系统，其内在动力学很难阐明。在这里，我们报告了粗粒化分子模拟，这些模拟允许在热力学平衡条件下研究超分子聚合物，明确显示了这些系统的复杂性质，这些系统由极其动态的分子实体组成。对分子交换的详细研究提供了对控制组装体如何相互通信的关键因素的深入了解，从而定义了系统的平衡动力学。使用最小化和更精细的具有化学相关性的分子模型，我们观察到，在这种自组装系统中存在丰富的协同复杂性。这为超分子聚合物系统提供了一个新的动态和概率（而不是结构）图景，其中，移动的分子物种不断地塑造在平衡时统计出现的组装体。
