Polyethyleneimine-grafted boronate affinity materials for selective enrichment of cis-diol-containing compounds

• A PEI-grafted boronate affinity material was synthesized.
• The binding pH was found to be as low as pH 4.5.
• Different binding pH can be attributed to the strong electrostatic repulsion.
• A separation system was developed based on boronate affinity chromatography, C18-RP chromatography and pCEC.
• SiO2@PEI–AAPBA-based SPE technology was applied to the purification of ribonucleosides.

Polyethyleneimine (PEI)-grafted and 3-acrylamidophenylboronic acid (AAPBA)-functionalized SiO2 boronate affinity materials were synthesized for the selective enrichment of cis-diol-containing compounds. Characterization results of scanning electron microscopy, Fourier transform infrared spectroscopy, elemental analysis, zeta potential, and X-ray photoelectron spectroscopy indicated the successful fabrication of SiO2@PEI–AAPBA materials. Chromatographic separation of test mixtures reveals that SiO2@PEI–AAPBA has high selective enrichment ability for cis-diol-containing compounds. The binding pH between SiO2@PEI–AAPBA and catechol was found to be as low as pH 4.5, while that between SiO2@PEI–AAPBA and adenosine was only ~7.5. This difference might be attributed to the strong electrostatic repulsion between the solid phase and analytes at a low pH. Furthermore, a diphasic separation column was fabricated based on boronate affinity chromatography, C18-reversed-phase chromatography and applied in pressurized capillary electrochromatography (pCEC). Results showed that four polar nucleosides could be well captured by the boronate affinity chromatography (BAC) section and separated by reversed phase pCEC. Finally, SiO2@PEI600–AAPBA-based solid-phase extraction technology was applied to the purification of ribonucleosides in real urine samples, and results of UHPLC–MS/MS revealed that the intensities of the extracted ions (a neutral mass loss of m/z 132.04 Da) of the ribonucleosides were significantly enhanced after the enrichment.

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