Multidentate boronate magnetic adsorbent assembled with polyhedral oligomeric silsesquioxanes and intramolecular diboronic acid for improving the binding strength toward glycoproteins.

Boronate affinity is an important method for the enrichment and separation of cis-diol containing compounds, but most of the conventional boronate materials suffer from weak binding strength as well as low binding capacity towards glycoproteins due to the use of single boronic acids as ligands. In this work, a novel multidentate boronate magnetic adsorbent was assembled by using amined polyhedral oligomeric silsesquioxane as spacer and a diboronic acid as ligand. The specially designed adsorbent exhibited high adsorption capacity for cis-diols due to the high density of phenylbronic acid moieties. More interestingly, the dissociation constants toward glycoproteins on the material were lowered to be ∼10 M, being at least 3 orders lower than the single boronic acid bonded adsorbents. By comparing the binding properties of small molecules containing one and two pairs of cis-diols, the enhanced binding strength of glycoproteins on the multidentate boronate magnetic adsorbent was attributed to the synergistic binding of glycoproteins on the special interface. The new materials successfully captured glycoproteins from 1000-fold diluted egg white, suggesting that the material could be an optional alternative adsorbent for enriching trace glycoproteins from complex bio-samples.