Effects of Knot Tightness at the Molecular Level

Liang Zhang, Jean-Francois Lemonnier, Angela Acocella, Matteo Calvaresi, Francesco Zerbetto, David Leigh

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    Abstract

    Three 819 knots in closed-loop strands of different lengths (approximately 20, 23 and 26 nm) were used to experimentally assess the consequences of knot tightness at the molecular level. Through the use of 1H nuclear magnetic resonance (NMR), diffusion ordered spectroscopy (DOSY), circular dichroism (CD), collision induced dissociation mass spectrometry (CID-MS) and molecular dynamics (MD) simulations on the different sized knots, we find that the structure, dynamics and reactivity of the molecular chains are dramatically affected by the tightness of the knotting. The tautness of entanglement causes differences in conformation, enhances the expression of topological chirality, weakens covalent bonds, inhibits decomplexation events and changes absorption properties. Understanding the effects of tightening nanoscale knots may usefully inform the design of knotted and entangled molecular materials.
    Original languageEnglish
    Pages (from-to)2452-2457
    Number of pages6
    JournalProceedings of the National Academy of Sciences
    Volume116
    Issue number7
    Early online date25 Jan 2019
    DOIs
    Publication statusPublished - 25 Jan 2019

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