Model for stretching elastic biopolymers which exhibit conformational transformations.

We derive an expression that represents the physical behavior of a polysaccharide molecule as it is stretched from the entropic region, through one or more ring conformational transformations, into the Hookean regime. The model adapts existing models in order to accommodate one or more force-induced conformational transformations of the glycan rings and is based on the concept of equilibrium between the clicked (longer conformers) and unclicked states. This equilibrium is determined by the Gibbs energy difference between these two states which is perturbed in favor of the clicked states by the force applied to the molecule. The derived expression is used to generate force-extension curves for model polymers and can illustrate the effect of the Gibbs energy for each transformation on the shape of these curves. It is also used to fit the force-extension curves of polysaccharides to obtain the Gibbs energy differences between the conformers. Good agreement was found between this model and experimental data on carboxymethylamylose, dextran, alginate, and pectin.