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.
Mechanical tightening of a synthetic molecular knot / Calvaresi M.; Duwez A.-S.; Leigh D.A.; Sluysmans D.; Song Y.; Zerbetto F.; Zhang L.. - In: CHEM. - ISSN 2451-9308. - ELETTRONICO. - 9:1(2023), pp. 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.File | Dimensione | Formato | |
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