Knots “choke off” polymers upon stretching

Long polymer chains inevitably get tangled into knots. Like macroscopic ropes, polymer chains are substantially weakened by knots and the rupture point is always located at the “entry” or “exit” of the knot. However, these phenomena are only poorly understood at a molecular level. Here we show that...

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Hauptverfasser: Neudecker, Tim (VerfasserIn) , Dreuw, Andreas (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 5 January 2016
In: Angewandte Chemie. International edition
Year: 2016, Jahrgang: 55, Heft: 2, Pages: 811-814
ISSN:1521-3773
DOI:10.1002/anie.201508706
Online-Zugang:Verlag, Volltext: http://dx.doi.org/10.1002/anie.201508706
Verlag, Volltext: http://onlinelibrary.wiley.com/doi/10.1002/anie.201508706/abstract
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Verfasserangaben:Tim Stauch and Andreas Dreuw

MARC

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520 |a Long polymer chains inevitably get tangled into knots. Like macroscopic ropes, polymer chains are substantially weakened by knots and the rupture point is always located at the “entry” or “exit” of the knot. However, these phenomena are only poorly understood at a molecular level. Here we show that when a knotted polyethylene chain is tightened, most of the stress energy is stored in torsions around the curved part of the chain. The torsions act as “work funnels” that effectively localize mechanical stress in the immediate vicinity of the knot. As a result, the knot “chokes” the chain at its entry or exit, thus leading to bond rupture at much lower forces than those needed to break a linear, unknotted chain. Our work not only explains the weakening of the polymer chain and the position of the rupture point, but more generally demonstrates that chemical bonds do not have to be extensively stretched to be broken. 
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