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Thermodynamics of complex formation between hydroxypropyl-β-cyclodextrin and quercetin in water–ethanol solvents at T = 298.15 K

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Abstract

Quercetin (QCT) is a flavonoid possessing many activities, such as neuro-/cardioprotective, anti-inflammatory and anticancer, but its pharmacological application is severely curtailed by its low water solubility and in vivo bioavailability. The formation of a QCT–hydroxypropyl-β-cyclodextrin (HPβCD) host–guest complex is promising to improve QCT therapeutic potential. Therefore, here the heat effects of HPβCD solutions with QCT solutions in water–ethanol solvents at different concentrations were studied by calorimetric titration, and the stability of molecular complexes was assessed by UV–Vis spectrophotometry. Calorimetric titrations revealed the formation of a QCT/HPβCD host–guest complex with a stoichiometric ratio of 1:1 in X(EtOH) = 0.00, 0.05 and 0.10 molar fractions of solvents at pH = 7.0 and pH = 8.1. Thermodynamic parameters of the complex formation reaction (lgK; ΔrH; TΔrS) were obtained in these experimental conditions. Differently, no complex formation was noticed in water–ethanol mixed solvent when ethanol volume fraction exceeded 0.2 at neutral and alkaline pH, as well as a volume fraction higher than 0.1 at acidic pH. Furthermore, the results of differential scanning calorimetry tests run on dried HPβCD after dissolution in hydroalcoholic solutions indicated that ethanol and water compete for the complexation within the hydrophobic cavity of HPβCD. This explains the decreased QCT complexation efficacy in the presence of ethanol beyond 0.1 or 0.2 volume fraction.

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Acknowledgements

The calorimetric measurements presented in this work were carried out at the Institute of Thermodynamics and Kinetics of Chemical Processes of the Ivanovo State University of Chemistry and Technology (ISUCT) using the equipment of the Center for Collective Use of ISUCT. The study was carried out under grant of Council on grants of the President of the Russian Federation (Project 14.Z56.18.877-MK). The authors thank the University of Naples Federico II for the financial support of their collaboration contributed to the preparation of this paper.

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Authors and Affiliations

  1. Department of General Chemical Technology, Faculty of Inorganic Chemistry and Technology, Ivanovo State University of Chemistry and Technology, Sheremetevsky Avenue 7, Ivanovo, Russian Federation, 153000

    Tatiana Usacheva, Dzhovidon Kabirov, Diana Beregova, George Gamov & Valentin Sharnin

  2. Department of Pharmacy, University of Naples Federico II, Via Domenico Montesano 49, 80131, Naples, Italy

    Marco Biondi, Laura Mayol, Federica D’Aria & Concetta Giancola

  3. Interdisciplinary Research Centre on Biomaterials – CRIB, Università di Napoli Federico II, P.le Tecchio, 80, Naples, Italy

    Marco Biondi & Laura Mayol

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  1. Tatiana Usacheva
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Correspondence to Tatiana Usacheva.

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Usacheva, T., Kabirov, D., Beregova, D. et al. Thermodynamics of complex formation between hydroxypropyl-β-cyclodextrin and quercetin in water–ethanol solvents at T = 298.15 K. J Therm Anal Calorim 138, 417–424 (2019). https://doi.org/10.1007/s10973-019-08136-5

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