Preparation and characterization of fluorophenylboronic acid-functionalized monolithic columns for high affinity capture of cis-diol containing compounds

• Published in: Journal of Chromatography A Vol. 1305; pp. 123 - 130
• Main Authors: Li, Qianjin, Lü, Chenchen, Liu, Zhen
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 30.08.2013; Elsevier
• Subjects: acids; Affinity; Analytical chemistry; Binding; binding capacity; Biological and medical sciences; Boronate affinity; Boronic Acids - chemistry; Capture; Chemistry; Chromatographic methods and physical methods associated with chromatography; chromatography; Chromatography, Affinity - instrumentation; Cis-diol; Enrichment; Exact sciences and technology; Fluorine - chemistry; Fluorophenylboronic acid; Glycoprotein; glycoproteins; humans; Hydrogen-Ion Concentration; Investigative techniques, diagnostic techniques (general aspects); Ligands; Medical sciences; Microscopy, Electron, Scanning; Miscellaneous. Technology; molecular weight; Monolithic columns; monosaccharides; Nucleosides; Other chromatographic methods; Pathology. Cytology. Biochemistry. Spectrometry. Miscellaneous investigative techniques; Spacers; Urine; Cis-diol; Fluorophenylboronic acid; Boronate affinity; Monolithic columns; Capture; Biological fluid; Chemical analysis; Chromatographic retention; Micellar electrokinetic capillary chromatography; Esterases; Pyrocatechol; Diphenols; Chemical enrichment; Surface structure; Affinity adsorbent; Characterization; Clinical biology; Nucleoside; Trace analysis; Human; Urine; Scanning electron microscopy; Diol; Healthy subject; Enzyme; Monolithic column; Morphology; Preparation; Hydrolases; Boron Organic compounds; Pancreatic ribonuclease; Boronic acids
• DOI: 10.1016/j.chroma.2013.07.007
• ISSN: 0021-9673

•Three fluorophenylboronic acid-functionalized monoliths were prepared.•The monoliths exhibited untrahigh boronate affinity toward cis-diol compounds.•The boronate affinity was strongly influenced by spacer arm length.•The monolith with appropriate spacer arm length can bind with cis-diols at pH 6.0. Boronic acids are important ligands for the selective recognition and capture of cis-diol containing compounds, such as nucleosides and glycoproteins. In a recent study, it was found that 2,4-difluoro-3-formyl-phenylboronic acid (DFFPBA) exhibited an ultrahigh boronate affinity for binding with monosaccharides. Herein three DFFPBA-functionalized monolithic columns with varying spacer arms were synthesized and characterized. Different cis-diol containing compounds were used for the evaluation of the boronate affinity of the DFFPBA-functionalized monoliths. The DFFPBA-functionalized monoliths exhibited advantageous characteristics. These monoliths exhibited an ultrahigh boronate affinity toward cis-diol containing compounds. Moreover, the monolith with appropriate spacer arm exhibited a low binding pH (6.0) for cis-diols of small molecular weight. These advantages made DFFPBA-functionalized monoliths suitable for the enrichment of trace cis-diol containing compounds in neutral and weak acidic real samples. In addition, it was interesting that the length of spacer arms strongly influenced the boronate affinity: increasing the spacer arm resulted in apparently reduced boronate affinity, and inappropriate spacer arm length even eliminated the boronate affinity toward glycoprotein. To explain such a phenomenon, a possible mechanism was proposed. Finally, the potential of DFFPBA-functionalized monoliths for real applications was demonstrated with the selective enrichment of modified nucleosides from human urine.