How to understand the ensemble equivalence during stretching of a single macromolecule

Abstract

In this paper, we discuss the elastic behavior of an isolated macromolecule in conjugated and non-conjugated ensembles during different modes of applying a mechanical force to the chain ends, namely, the mechanical effects corresponding to the methods of atomic force microscopy, magnetic levitation, and stretching of a macromolecule in an isotropic force field. Recently published results on the Langevin dynamics computer simulation of the stretching of a Gaussian polymer chain in different ensembles are analyzed. An analytical description of all the results of this simulation is given to show that the conclusion made by the authors of those studies about the nonequivalence of conjugated ensembles for Gaussian chains is not quite correct. A theoretical examination of the stretching of individual semirigid chains, which exhibit interesting behavior because of manipulations with actin molecules and microtubules, which are components of the cytoskeleton of most cells, is performed. We present rigorous analytical results about the stretching of chains composed of two or three freely jointed rods of equal length without consideration for excluded-volume inter-actions. It is shown that the stress-strain curves of these chains differ not only quantitatively but also qualitatively in different ensembles and that these curves for a chain of two freely jointed rods have an anomalous shape. These results on the different behavior of stress-strain for different modes of external mechanical impacts can be useful for interpreting experiments on the stretching of individual polymer molecules with different structures obtained via different methods, such as atomic-force microscopy and magnetic levitation.