Discovering privileged topologies of molecular knots with self-assembling models

Area of Science:

• Supramolecular Chemistry
• Computational Chemistry
• Materials Science

Background:

• Synthesizing complex molecular knots is challenging, with limited known topologies.
• Existing methods for creating supramolecular constructs have not significantly expanded the diversity of molecular knots.

Purpose of the Study:

• To identify novel, thermodynamically and kinetically accessible molecular knot topologies.
• To explore designable topologies for supramolecular self-assembly.

Main Methods:

• Utilized Monte Carlo sampling and molecular dynamics simulations.
• Applied principles of supramolecular assembly and exhaustive enumeration of braiding patterns.
• Investigated knot types based on helical templates and general geometries.

Main Results:

• Identified a restricted set of admissible topologies for synthetic knots.
• Found that only specific shapes possess the required closed, symmetric, and quasi-planar characteristics.
• Discovered novel complex molecular knots, including 10₁₂₄ and 15n₄₁₁₈₅, in addition to known ones.

Conclusions:

• Computational methods can effectively discover new molecular knot topologies.
• The study provides a curated collection of accessible molecular knots, including novel complex structures.
• The identified knots are prime candidates for future experimental synthesis via self-assembly.