Preparation of restricted-access boronate affinity adsorbent with excellent anti-protein adsorption property for directly extracting small cis-diol molecules from biological matrices

Boronate affinity adsorbents are of great promise in the enrichment of small cis-diol-containing molecules (cis-diols) from biological matrices. This work develops a restricted-access boronate affinity mesoporous adsorbent, in which boronate sites are only distributed on the internal surface of mesopores and the external surface is a strongly hydrophilic layer. The adsorbent has high binding capacities (30.3 mg g-1, 22.9 mg g-1 and 14.9 mg g-1 for dopamine, catechol and adenosine, respectively) in spite of removal of the boronate sites on the external surface of adsorbent. The adsorption specific of adsorbent towards cis-diols was assessed by dispersive solid-phase extraction (d-SPE) method, and the results show that the adsorbent can selectively extract small cis-diols in the biosamples while exclude proteins completely. Under the optimal d-SPE, the nucleosides and cis-diol drugs in human serum were successfully analyzed by coupling d-SPE with high-performance liquid chromatography. Where, the detection limits are between 6.1 and 13.4 ng mL-1 for four nucleosides, and 24.9 and 34.3 ng mL-1 for two cis-diol drugs; the relative recoveries of all the analytes vary from 84.1% to 110.1% (RSDs <13.4%, n = 6). The results indicate that the adsorbent can directly treat the real biosamples without the necessary protein precipitation steps in advance, thus simplifying the analysis process.