Single-molecule elasticity measurements of the onset of excluded volume in poly(ethylene glycol)

A polymer must reach a certain size to exhibit significant excluded-volume interactions and adopt a swollen random-walk configuration. We show that single-molecule measurements can sense the onset of swelling by modulating the effective chain size with force: as the force is reduced from a large value, the polymer is first highly aligned, then a Gaussian coil, then finally a swollen chain, with each regime exhibiting a distinct elasticity. We use this approach to quantify the structural parameters of poly(ethylene glycol) and show that they vary in the expected manner with changes in solvent.