Single polymer mechanics across the force regimes

Abstract

I review theoretical and experimental results on the force-extension response of single polymers, with a focus on scaling pictures of low-force elastic regimes, and recent measurements of synthetic and biological chains that explore those regimes. The mechanical response of single polymers is an old theoretical problem whose exploration was instigated by the curious thermomechanical behavior of rubber. Up until the 1990s, the main utility of those calculations was to explain bulk material mechanics. However, in that decade, it became possible to directly test the calculations through high-precision single-chain stretching experiments (i.e., force spectroscopy). I present five major single-chain elasticity models, including scaling results based on blob-chain models, along with analytic results based on linear response theory, and those based on freely jointed chain or worm-like chain structure. Each model is discussed in terms of the regime of force for which it holds, along with the status of its rigorous assessment with experiment. Finally, I show how the experiments can provide new insight into polymer structure itself, with particular emphasis on polyelectrolytes.