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Dithiane Based Boronic Acid as a Carbohydrate Sensor in an Aqueous Solution at pH 7.5: Theoretical and Experimental Approach

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Abstract

Carbohydrate sensing in an aqueous solution remains a very challenging area of interest. Using the idea of covalent reversible interaction between boronic acids and the diol groups in carbohydrates enable us to design a carbohydrate sensor 1-thianthrenylboronic acid (1T), which has high selectivity towards fructose. To elucidate the sensing and binding properties of 1T with sugars, we have incorporated theoretical (DFT and TD-DFT) and spectroscopic techniques. For an optimized geometry, the complete vibrational assignments were done with FT-IR and FT-Raman spectra. Physiochemical parameters were obtained by implementing frontier molecular orbital (FMO) analysis. Further, excited state properties were determined by performing TD-DFT calculations in solvent and these properties were in good agreement with the experiment. The steady state fluorescence measurements with varying concentration of sugars, revealed that the fluorescence intensity of boronic acid is enhanced by studied sugars due to the structural modification. We also noticed remarkable changes in fluorescence lifetimes and quantum yield after adding sugars. The article also reports influence of pH on boronic acid’s fluorescence intensity with and without sugars. The fluorescence of boronic acid increases with the increase in pH. These changes are due to acid–base equilibrium of boronic acid and led us to estimate the pKa value of 7.6. All the theoretical and experimental evidences suggested that 1T can be used as a possible fluorescent sensor for fructose. In addition, 1T showed very good affinity for Cu2+ ion with Ka = 150 × 102 M−1, which suggests that 1T can also be used as a chemosensor for Cu2+ ions.

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Acknowledgements

The author would like to thank “Karnataka Science and Technology Promotion Society (K-STePS), Department of Science and Technology (DST) and Government of Karnataka” for providing financial support to carry out this research. The authors would like to thank Sophisticated Analytical Instrumentation facility (SAIF), Indian Institute of Technology, Madras, for providing FT-IR, FT-Raman spectra and single crystal X-ray diffraction data. And also, University with Potential for Excellence (UPE) University of Mysore for providing, fluorescence and UV-absorption spectrometer facility. We would like to thank Dr. Jeyaseelan S., for providing computational facility.

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  1. Department of Studies in Physics, University of Mysore, Mysuru-570006, Manasagangotri, Karnataka, India

    Bhavya Nelligere Revanna & Mahendra Madegowda

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Correspondence to Mahendra Madegowda.

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Revanna, B.N., Madegowda, M. Dithiane Based Boronic Acid as a Carbohydrate Sensor in an Aqueous Solution at pH 7.5: Theoretical and Experimental Approach. J Fluoresc 31, 1683–1703 (2021). https://doi.org/10.1007/s10895-021-02791-4

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