Abstract
Quite often polymers exhibit different elastic behavior depending on the statistical ensemble (Gibbs vs. Helmholtz). This is an effect of strong fluctuations. In particular, two-state polymers, which locally or globally fluctuate between two classes of microstates, can exhibit strong ensemble inequivalence with negative elastic moduli (extensibility or compressibility) in the Helmholtz ensemble. Two-state polymers consisting of flexible beads and springs have been studied extensively. Recently, similar behavior was predicted in a strongly stretched wormlike chain consisting of a sequence of reversible blocks, fluctuating between two values of the bending stiffness (the so called reversible wormlike chain, rWLC). In this article, we theoretically analyse the elasticity of a grafted rod-like semiflexible filament which fluctuates between two states of bending stiffness. We consider the response to a point force at the fluctuating tip in both the Gibbs and the Helmholtz ensemble. We also calculate the entropic force exerted by the filament on a confining wall. This is done in the Helmholtz ensemble and, under certain conditions, it yields negative compressibility. We consider a two-state homopolymer and a two-block copolymer with two-state blocks. Possible physical realizations of such a system would be grafted DNA or carbon nanorods undergoing hybridization, or grafted F-actin bundles undergoing collective reversible unbinding.
| Original language | English |
|---|---|
| Article number | 2307 |
| Journal | Polymers |
| Volume | 15 |
| Issue number | 10 |
| DOIs | |
| State | Published - May 2023 |
Keywords
- elasticity
- negative compressibility
- statistical ensemble inequivalence
- wormlike chain
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