Little is known regarding the effects of knotting on the mechanical properties of individual molecules. Here, we report on the force response of discrete synthetic small-molecule trefoil knots upon tightening. By combining single-molecule force spectroscopy with quantum chemical calculations, we provide evidence for the mechanism of tightening. It is associated with a higher resisting force than for larger protein knots and is modulated by the chemical environment. The central metal coordination plays a crucial role in the tightening process, as well as in the reverse process that recovers the initial knotted conformation. As a result of the compact structure, the recovery of conformation after mechanical perturbation is very fast. The tightening also plays an important role in accommodating mechanical stress. It provides a reserve of extensibility; the extra energy that the knotted strand can absorb in comparison with an unknotted strand is ∼13 kcal mol−1.

Calvaresi M., Duwez A.-S., Leigh D.A., Sluysmans D., Song Y., Zerbetto F., et al. (2023). Mechanical tightening of a synthetic molecular knot. CHEM, 9(1), 65-75 [10.1016/j.chempr.2022.12.014].

Mechanical tightening of a synthetic molecular knot

Calvaresi M.;Zerbetto F.;
2023

Abstract

Little is known regarding the effects of knotting on the mechanical properties of individual molecules. Here, we report on the force response of discrete synthetic small-molecule trefoil knots upon tightening. By combining single-molecule force spectroscopy with quantum chemical calculations, we provide evidence for the mechanism of tightening. It is associated with a higher resisting force than for larger protein knots and is modulated by the chemical environment. The central metal coordination plays a crucial role in the tightening process, as well as in the reverse process that recovers the initial knotted conformation. As a result of the compact structure, the recovery of conformation after mechanical perturbation is very fast. The tightening also plays an important role in accommodating mechanical stress. It provides a reserve of extensibility; the extra energy that the knotted strand can absorb in comparison with an unknotted strand is ∼13 kcal mol−1.
2023
Calvaresi M., Duwez A.-S., Leigh D.A., Sluysmans D., Song Y., Zerbetto F., et al. (2023). Mechanical tightening of a synthetic molecular knot. CHEM, 9(1), 65-75 [10.1016/j.chempr.2022.12.014].
Calvaresi M.; Duwez A.-S.; Leigh D.A.; Sluysmans D.; Song Y.; Zerbetto F.; Zhang L.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/948764
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