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Direct analysis of polyols using 3-nitrophenylboronic acid in capillary electrophoresis: thermodynamic and electrokinetic principles of molecular recognition

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Abstract

The design of boronic acid sensors for photometric detection of carbohydrates has relied on exploiting differences in the thermodynamic stability of complex formation for molecular recognition. Herein, we introduce a direct method for analysis of sugar alcohols using 3-nitrophenylboronic acid (NPBA) as an electrokinetic probe in capillary electrophoresis (CE). Dynamic complexation of neutral polyols by NPBA during electromigration allows for their simultaneous resolution and UV detection based on formation of an anionic ternary boronate ester complex in phosphate buffer. Unlike conventional boronic acid sensors, thermodynamic and electrokinetic processes in CE allow for improved selectivity for the resolution of sugar alcohol stereoisomers having different vicinal polyol chain lengths even in cases when binding affinity is similar due to differences in their complex mobility. Three complementary approaches were investigated to compare the thermodynamics of polyol chelation with NPBA, namely direct binding assays by CE, UV absorbance spectroscopy and an indirect pK a depression method. Overall, CE offers a convenient platform for characterization of reversible arylboronic acid interactions in free solution while allowing for direct analysis of complex mixtures of neutral/UV-transparent polyols without complicated sample handling.

3-nitrophenylboronic acid (NPBA) functions as an electrokinetic probe in capillary electrophoresis for the separation and detection of polyols based on dynamic ternary boronate ester complexation in free solution.

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Abbreviations

CE:

Capillary electrophoresis

∆λ max :

Change in peak absorbance wavelength

∆pK a :

Change in apparent weak acidity equilibrium constant

EOF:

Electroosomotic flow

f AC :

Fraction of tetrahedral boronate ester complex

K :

Conditional formation constant

μ Aep :

Apparent electrophoretic mobility

μ ep AC :

Complex electrophoretic mobility

NPBA:

3-nitrophenylboronic acid

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Acknowledgments

Financial support for this research was provided by the Natural Science and Engineering Council of Canada. P.B.M. also wishes to acknowledge support in the form of a Japan Society for Promotion of Science—Invited Fellowship.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, L8S 4M1, Canada

    Fan Fei & Philip Britz-McKibbin

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  1. Fan Fei
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  2. Philip Britz-McKibbin
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Correspondence to Philip Britz-McKibbin.

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Fei, F., Britz-McKibbin, P. Direct analysis of polyols using 3-nitrophenylboronic acid in capillary electrophoresis: thermodynamic and electrokinetic principles of molecular recognition. Anal Bioanal Chem 398, 1349–1356 (2010). https://doi.org/10.1007/s00216-010-4038-4

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  • DOI: https://doi.org/10.1007/s00216-010-4038-4

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