We present a new framework for the description of macromolecules subject to confining geometries. The two main ingredients are a new computational method and the definition of a new molecular size parameter. The computational method, hereafter referred to the confinement analysis from bulk structures (CABS), allows the computation of equilibrium partition coefficients as a function of confinement size solely based on a single sampling of the configuration space of a macromolecule in bulk. Superior in computational speed to previous computational methods, CABS is capable of handling slits, channels, and box confining geometries for all molecular architectures. The new molecular size parameter, hereafter referred to the steric exclusion radius Rs, is explicitly defined and computed for a number of rigid objects and flexible polymers. We suggest that Rs is the relevant molecular size parameter for characterization of spatial confinement effects on macromolecules. Results for the equilibrium partition coefficient in the weak confinement regime depend only on the ratio of Rs to the confinement size regardless of molecular details.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry