1 research outputs found
Theory of mechanical unfolding of homopolymer globule: all-or-none transition in force-clamp mode vs phase coexistence in position-clamp mode
Equilibrium mechanical unfolding of a globule formed by long flexible
homopolymer chain collapsed in a poor solvent and subjected to an extensional
force f (force-clamp mode) or extensional deformation D (position-clamp mode)
is studied theoretically. Our analysis, like all previous analysis of this
problem, shows that the globule behaves essentially differently in two modes of
extension. In the force-clamp mode, mechanical unfolding of the globule with
increasing applied force occurs without intramolecular microphase segregation,
and at certain threshold value of the pulling force the globule unfolds as a
whole ("all-or-none" transition). The value of the threshold force and the
corresponding jump in the distance between the chain ends increase with a
deterioration of the solvent quality and/or with an increase in the degree of
polymerization. In the position-clamp mode, the globule unfolding occurs via
intramolecular microphase coexistence of globular and extended microphases
followed by an abrupt unraveling transition. Reaction force in the microphase
segregation regime demonstrates an "anomalous" decrease with increasing
extension. Comparison of deformation curves in force and position-clamp modes
demonstrates that at weak and strong extensions the curves for two modes
coincide, differences are observed in the intermediate extension range. Another
unfolding scenario is typical for short globules: in both modes of extension
they unfold continuously, without jumps or intramolecular microphase
coexistence, by passing a sequence of uniformly elongated configurations.Comment: 19 pages, 13 figures, 1 tabl