Fabrication of ionic liquid functionalized silica with different anions and the application in mixed-mode and chiral chromatography

To realize the potential of ionic liquid functionalized silica to prepare mixed-mode and chiral stationary phases, two ionic liquid silane reagents with different anions were synthesized via a high-efficiency click reaction. Then they were decorated onto the surface of silica by a one-step bonding reaction. The functionalized silica was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and elemental analysis (EA). Two stationary phases provided satisfactory performance when compared with a commercial mixed-mode column. Notably, Sil-C10Im-D-BCS with D-3-bromocamphor-8-sulfonate (D-BCS) as anion presented chiral separation capacity towards 1,2,3,4-Tetrahydro-1-naphthol. The separation mechanism was investigated through multiple pathways, and the results revealed that the prepared stationary phases can retain and separate solutes through multiple interactions, like hydrophobic effect, ion exchange, hydrogen-bond interaction, etc. Quantum chemical calculation (QC) was employed to obtain the optimized structures and the binding energy of anions to cations. The results provided some insights into the retention mechanism from a molecular perspective. This work demonstrated the superiority of ionic liquid functionalized silica as mixed-mode stationary phases and the potential of chiral ionic liquid as chiral selectors.