Theoretical and Computational Chemistry

A Complete Structural and Dynamic Characterization of Supramolecular Polymers via Automatic Learning of Defects


A central paradigm of self-assembly is to create ordered structures starting from molecular monomers that spontaneously recognize and interact with each other via noncovalent interactions. In the recent years, great efforts have been directed toward reaching the perfection in the design of a variety of supramolecular polymers and materials with different architectures. The resulting structures are often thought of as ideally perfect, defect-free supramolecular fibers, micelles, vesicles, etc., having an intrinsic dynamic character, which are typically studied at the level of statistical ensembles to assess their average properties. However, high-resolution molecular simulations recently demonstrated that local defects that may be present or may form in these assemblies, and which are poorly captured by conventional approaches, are key to controlling their dynamic behavior and properties. The study of these defects poses considerable challenges, as the flexible/dynamic nature of these soft systems makes it difficult to identify what effectively constitutes a defect, and to characterize its stability and evolution. Here, we demonstrate the power of unsupervised machine learning techniques to systematically identify and compare defects in supramolecular polymer variants in different conditions, using as a benchmark high-resolution molecular simulations of a family of supramolecular polymers. We shot that this approach allows a complete data-driven characterization of the internal structure and dynamics of these complex assemblies and of the dynamic pathways for defects formation and resorption. This provides a useful, generally applicable approach to unambiguously identify defects in these dynamic self-assembled materials and to classify them based on their structure, stability and dynamics.

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Submitted preprint version


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