Performance of functionalized monolithic silica capillary columns with different mesopore sizes using radical polymerization of octadecyl methacrylate

• Published in: Journal of Chromatography A Vol. 1651; p. 462282
• Main Authors: Hara, Takeshi, Baron, Gino V., Hata, Kosuke, Izumi, Yoshihiro, Bamba, Takeshi, Desmet, Gert
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 16.08.2021
• Subjects: Column efficiency; Mesopore size; Monolithic silica; Phase ratio; Radical polymerization; Retention; Phase ratio; Column efficiency; Monolithic silica; Mesopore size; Retention; Radical polymerization
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2021.462282

•Octadecyl methacrylate (ODM) was re-tested to functionalize silica monoliths.•ODM-monoliths with 3 different mesopore sizes can be prepared without clogging.•The present ODM-monoliths show an enhanced retention compared to literature.•The efficiency (H = 6 μm) is higher than that of the ODM-columns in literature (H = 10 μm).•ODM-phase showed a lower diffusivity than ODS-phase, explaining the steeper C-term. We report on the possibility to enhance the phase ratio and retention factor in silica monoliths. According to pioneering work done by Núñez et al. [1], this enhancement is pursued by applying a stationary phase layer via radical polymerization with octadecyl methacrylate (ODM) as an alternative to the customary octadecylsilylation (C18-derivatization). The difference in band broadening, retention factor and separation selectivity between both approaches was compared. Different hydrothermal treatment temperatures for the column preparation were applied to produce monolithic silica structures with three different mesopore sizes (resp. 10, 13, and 16 nm, as determined by argon physisorption) while maintaining similar domain size (sum of through-pore and skeleton size). It has been found that the columns with the poly(octadecyl methacrylate)-phase (ODM columns) provided a 60 to 80% higher retention factor in methanol-water mixture compared to the octadecylsilylated (ODS) columns produced by starting from similar silica backbone structures. In acetonitrile-water mixture, the enhancement is smaller (15 to 30% times higher), yet significant. By adjusting the fabrication conditions (for both the preparation of the monolithic backbones and the surface functionalization), the achieved retention factors (up k = 4.89 for pentylbenzene in 80:20% (v/v) methanol/water) are obviously higher than obtained in the pioneering study on ODM monoliths of Núñez et al. [1], and column clogging could be completely avoided. In addition, also separation efficiencies were significantly higher than shown in Ref. [1], with plate heights as low as 5.8 μm. These plate heights are however inferior to those observed on the ODS-modified sister columns. The difference can be explained by the slower intra-skeleton diffusion displayed by the ODM-modified columns, in turn caused by the larger obstruction to diffusion originating from the thicker stationary phase layer.