Transport properties and size exclusion effects in wide-pore superficially porous particles

The relative importance of convection and diffusion are found to depend on the molecule (tracer) size through the diffusion rate, and convection effects are more significant for larger, slower-diffusing molecules. When larger molecules are utilized, the intraparticle concentration is reduced in proportion to the local particle porosity, leading to a natural definition of the accessible porosity used in size exclusion chromatography (SEC). Although the pore shape is complex, the SEC constant K can be calculated directly from simulation. Simulation demonstrates that the effective diffusion coefficient is elevated near the particle hull, which is largely open to interstitial flow, and decreases with depth into the particle. All molecules studied here have transport access to the entire particle depth, although the accessible volume at a given depth depends on their size. The first passage time into the particle is well predicted by the diffusion rate, but residence time is influenced by convection, shortening the average visit duration. These results are of interest in “perfusion” chromatography where convection is thought to increase separation efficiency for large biomolecules.