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 recent years, great efforts have been directed toward perfecting 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, 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 5 Å resolution coarse-grained molecular simulations of a family of supramolecular polymers. We show 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.

Identifying and Tracking Defects in Dynamic Supramolecular Polymers

Bochicchio D.;
2020

Abstract

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 recent years, great efforts have been directed toward perfecting 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, 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 5 Å resolution coarse-grained molecular simulations of a family of supramolecular polymers. We show 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.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11567/1016817
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? 8
  • Scopus 24
  • ???jsp.display-item.citation.isi??? 25
social impact