Facile preparation of a stable and functionalizable hybrid monolith via ring-opening polymerization for capillary liquid chromatography

• A POSS-based functionalizable hybrid monolith was successfully prepared via ring-opening polymerization.
• The obtained hybrid monolith possesses well-controlled 3D skeleton.
• A column efficiency of 110,000 N/m was achieved for isocratic separation of alkylbenzenes.
• The obtained hybrid monolith showed high stability and good surface tailorability.

An organic–inorganic hybrid monolith was prepared by a single-step ring-opening polymerization of octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxane (POSS) with poly(ethylenimine) (PEI). The obtained hybrid monoliths possessed high ordered 3D skeletal microstructure with dual retention mechanism that exhibits reversed-phase (RP) mechanism under polar mobile phase and hydrophilic-interaction liquid chromatography (HILIC) retention mechanism under less polar mobile phase. The high column efficiencies of 110,000 N/m can be achieved for separation of alkylbenzenes in capillary reversed-phase liquid chromatography (cLC). Due to the robust property of hybrid monolith and the rich primary and secondary amino groups on its surface, the resulting hybrid monolith was easily modified with γ-gluconolactone and physically coated with cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC), respectively. The former was successfully applied for HILIC separation of neutral, basic and acidic polar compounds as well as small peptides, and the latter for enantioseparation of racemates in cLC. The high column efficiencies were achieved in all of those separations. These results demonstrated that the hybrid monolith (POSS–PEI) possessed high stability and good surface tailorbility, potentially being applied for other research fields