Knots modify the coil-stretch transition in linear DNA polymers

We perform single-molecule DNA experiments to investigate the relaxation dynamics of knotted polymers and examine the steady-state behavior of knotted polymers in elongational fields. The occurrence of a knot reduces the relaxation time of a molecule and leads to a shift in the molecule's coil-stretch transition to larger strain rates. We measure chain extension and extension fluctuations as a function of Weissenberg number for unknotted and knotted molecules. The curves for knotted molecules can be collapsed onto the unknot curves by defining an effective Weissenberg number based on the measured knotted relaxation time in the low extension regime, or a relaxation time based on Rouse/Zimm scaling theories in the high extension regime. Because a knot reduces a molecule's relaxation time, we observe that knot untying near the coil-stretch transition can result in the molecule experiencing both a stretch-coil transition with the knot, and coil-stretch transition without the knot, at the same strain rate.