  While stretching of most polymer chains leads to rather featureless
force-extension diagrams, some, notably DNA, exhibit non-trivial behavior with
a distinct plateau region. Here we propose a unified theory that connects
force-extension characteristics of the polymer chain with the convexity
properties of the extension energy profile of its individual monomer subunits.
Namely, if the effective monomer deformation energy as a function of its
extension has a non-convex (concave up) region, the stretched polymer chain
separates into two phases: the weakly and strongly stretched monomers.
Simplified planar and 3D polymer models are used to illustrate the basic
principles of the proposed model. Specifically, we show rigorously that when
the secondary structure of a polymer is mostly due to weak non-covalent
interactions, the stretching is two-phase, and the force-stretching diagram has
the characteristic plateau. We then use realistic coarse-grained models to
confirm the main findings and make direct connection to the microscopic
structure of the monomers. We demostrate in detail how the two-phase scenario
is realized in the \alpha-helix, and in DNA double helix. The predicted plateau
parameters are consistent with single molecules experiments. Detailed analysis
of DNA stretching demonstrates that breaking of Watson-Crick bonds is not
necessary for the existence of the plateau, although some of the bonds do break
as the double-helix extends at room temperature. The main strengths of the
proposed theory are its generality and direct microscopic connection.
