Pore volume accessibility of particulate and monolithic stationary phases

• Pore volume accessibility has been determined for particulate and monolithic stationary phases.
• Accessible pore volume was correlated to size of the exclusion pores.
• Column efficiency improves for smaller molecules with larger accessible pore volume.
• Suggested protocol is used to characterize pore formation in polymer monoliths.

A chromatographic characterization of pore volume accessibility for both particulate and monolithic stationary phases is presented. Size-exclusion calibration curves have been used to determine the pore volume fraction that is accessible for six alkylbenzenes and twelve polystyrene standards in tetrahydrofuran as the mobile phase. Accessible porosity has been then correlated with the size of the pores from which individual compounds are just excluded.I have determined pore volume accessibility of commercially available columns packed with fully and superficially porous particles, as well as with silica-based monolithic stationary phase. I also have investigated pore accessibility of polymer-based monolithic stationary phases. Suggested protocol is used to characterize pore formation at the early stage of the polymerization, to evaluate an extent of hypercrosslinking during modification of pore surface, and to characterize the pore accessibility of monolithic stationary phases hypercrosslinked after an early termination of polymerization reaction. Pore volume accessibility was also correlated to column efficiency of both particulate and monolithic stationary phases.