Abstract
The systematic investigations by Monte Carlo (MC) simulations of parameters involved in partitioning in size exclusion chromatography (SEC) are reported. Specifically, three realistic features involved in the separation mechanism are treated: (a) real chain features as contrast to ideal chain behavior, (b) finite concentration of macromolecules in partitioning, and (c) adsorption of polymer on pore walls. In all cases an enhancement of the partitioning relative to the ideal circumstances was found. The partitioning rules in these cases significantly deviate from the Casassa relation for ideal chains. The factors mentioned affect the shape of the universal calibration dependence and reduce its selectivity. The rationalization of the free energy of confinement in SEC based on a loss of orientational entropy of coil ellipsoids in a pore is suggested.
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