SpringerLink
Log in

Host–guest inclusion complex of β-cyclodextrin and benzoic acid in water–ethanol solvents: spectroscopic and thermodynamic characterization of complex formation

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

In this study, an inclusion complex of benzoic acid with β-cyclodextrin (BA-βCD) was obtained from water–ethanol solvents. The yield of complex synthesis in binary mixtures is greater than in water and reaches maximum value at 0.10 mol fraction of ethanol. Results of FTIR spectroscopy analysis showed that the main difference in the spectra of the acid and inclusion complex was observed in the frequency ranging from 2500 to 3100 cm−1, corresponding to aromatic hydrogen vibrations. These vibrations are highly attenuated in complex. Phase solubility and differential scanning calorimetry studies revealed that the inclusion complex was obtained with 1:1 stoichiometric ratio and the solubility of benzoic acid increased with an increase in β-cyclodextrin concentrations in water. The logarithm of stability constant in water was found to be lgK = 1.99. The thermodynamic parameters for the reaction of (BA-βCD) complex formation in H2O–EtOH solvents were determined from calorimetric experiments carried out by means of the calorimetric titration system TAM III (TA Instruments) at T = 25 °C. The heat effects of mixing β-cyclodextrin solutions with benzoic acid were obtained from water–ethanol mixed solvents containing X(EtOH) = (0.00, 0.10, 0.20 and 0.30) mole fraction at pH = 3.6 and T = 25 °C. However, at X(EtOH) = 0.30 mol fraction, according to the calorimetric titration data, no complex formation occurs. When transferring from H2O to H2O–EtOH solvents, complex stability decreases from lgK = 2.4 to lgK = 0.7, wherein the reaction exothermicity increases from − 12.2 kJ mol−1 to − 44.3 kJ mol−1. An increase in the exothermicity of complexation is accompanied by a decrease in the entropic contribution to the change in the reaction Gibbs energy.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Mendez SG, Espinar FJ, Alvarez AL, Longhi MR, Quevedo MA, Zoppi A. Ternary complexation of benzoic acid with β-cyclodextrin and aminoacids. Experimental and theoretical studies. J Incl Phenom Macrocycl Chem. 2016;85:33–48.

    CAS  Google Scholar 

  2. Terekhova I, Koz’biał M, Kumeev R, Gierycz P. Complex formation of native and hydroxypropylated cyclodextrins with benzoic acid in aqueous solution: volumetric and 1H NMR study. Chem Phys Lett. 2011;514:341–6.

    CAS  Google Scholar 

  3. Brewster ME, Vandecruys R, Peeters J, Neeskens P, Verreck G, Loftsson T. Comparative interaction of 2-hydroxypropyl-beta-cyclodextrin and sulfobutylether-beta-cyclodextrin with itraconazole: phase-solubility behavior and stabilization of supersaturated drug solutions. Eur J Pharm Sci. 2008;34(2–3):94–103.

    CAS  PubMed  Google Scholar 

  4. Yan H, ** L, Samuel HY. Solubilization of Fluasterone in cosolvent/cyclodextrin combinations. Int J Pharm. 2003;264:25–34.

    Google Scholar 

  5. Soares-Sobrinho JL, Santos FL, Lyra MA, Alves LD, Rolim LA, Lima AA, Nunes LC, Soares MF, Rolim-Neto PJ, Torres-Labandeira JJ. Benznidazole drug delivery by binary and multicomponent inclusion complexes using cyclodextrins and polymers. Carbohydr Polym. 2012;89(2):323–30.

    CAS  PubMed  Google Scholar 

  6. Challa R, Ahuja A, Ali J, Khar RK. Cyclodextrins in drug delivery: an updated review. AAPS Pharm Sci Tech. 2005;6:329–57.

    Google Scholar 

  7. Kustov AV, Smirnova NL, Neueder R, Kunz W. Amino acid solvation in aqueous kosmotrope solutions: temperature dependence of the L-Histidine-Glycerol interaction. J Phys Chem B. 2012;116:2325–9.

    CAS  PubMed  Google Scholar 

  8. Kustov AV. The aromatic amino acid behaviour in aqueous amide solutions—the temperature dependence of the L-phenylalanine-urea interaction. J Thermal Anal Calorim. 2007;89:841–6.

    CAS  Google Scholar 

  9. Donze C, Coleman AW. Solvent effects in competition between guest molecules for β-cyclodextrin. J Incl Phenom Mol Recogn Chem. 1995;23:11–21.

    CAS  Google Scholar 

  10. Yoshii H, Kometani T, Furuta T, Watanabe Y, Linko YY. Formation of inclusion complexes of cycldextrin with ethanol under anhydrous conditions. Biosci Biotechnol Biochem. 1998;62:2166–70.

    CAS  PubMed  Google Scholar 

  11. He Y, Li P, Yalkowsky SH. Solubilization of Fluasterone in cosolvent/cyclodextrin combinations. Inter J Pharm. 2003;264:25–34.

    CAS  Google Scholar 

  12. Zung JB, Munoz de la Pena A, Ndou TT, Warner IM. Influence of alcohol addition on the γ-CD: pyrene complex. J Phys Chem. 1991;95:6701–9.

    CAS  Google Scholar 

  13. Reer O, Muller BW. Investigation of the influence of cosolvents and surfactants on the complexation of dexamethasone with hydroxypropyl-β-cyclodextrin by use of a simplex lattice design. Eur J Pharm Biopharm. 1993;39:105–11.

    CAS  Google Scholar 

  14. Loftsson T, Ólafsdóttir BJ, Friðriksdóttir H, Jónsdóttir S. Cyclodextrin complexation of NSAIDs: physicochemical characteristics. Eur J Pharm Sci. 1993;1:95–101.

    CAS  Google Scholar 

  15. Pitha J, Hoshino T. Effect of ethanol on formation of inclusion complexes of hydroxypropylcyclodextrins with testosterone or with methyl orange. Inter J Pharm. 1992;80:243–51.

    CAS  Google Scholar 

  16. Belyakova A, Varvarin AM, Khora OV, Oranskaya EI. The Interaction of β-Cyclodextrin with benzoic acid. Russ J Phys Chem A. 2008;82:228–32.

    CAS  Google Scholar 

  17. Terekhova IV. Comparative thermodynamic study on complex formation of native and hydroxypropylated cyclodextrins with benzoic acid. Therm Acta. 2011;526:118–21.

    CAS  Google Scholar 

  18. Shimkin A. Optimization of DSC calibration procedure. Thermochim Acta. 2013;566:71–6.

    CAS  Google Scholar 

  19. Eysel W, Breuer KH. The calorimetric calibration of differential scanning calorimetry cells. Thermochim Acta. 1982;57:317–29.

    Google Scholar 

  20. Higuchi T, Connors KA. Phase-solubility techniques. Adv Anal Chem Instrum. 1965;4:117–2122.

    CAS  Google Scholar 

  21. Wadso I, Goldberg RN. Standard in isothermal microcalorimetry. Pure Appl Chem. 2001;73:1625–39.

    CAS  Google Scholar 

  22. Usacheva TR, Sharnin VA, Chernov IV, Matteoli E. Calorimetric investigation of the reaction of molecular complex formation of 18-crown-6 with D, L-alanine in water–ethanol mixtures. J Therm Anal Calorim. 2013;112:983–9.

    CAS  Google Scholar 

  23. Usacheva TR, Pham Thi L, Kuzmina KI, Sharnin VA. Thermodynamics of complex formation between Cu(II) and glycyl–glycyl–glycine in water–ethanol and water–dimethylsulfoxide solvent. J Therm Anal Calorim. 2017;130:471–8.

    CAS  Google Scholar 

  24. Usacheva TR, Pham Thi L, Terekhova IV, Kumeev RS, Sharnin VA. Application of isothermal titration calorimetry for evaluation of water-acetone and water-dimethylsulfoxide solvents influence on the molecular complex formation between 18-crown-6 and triglycine at 298.15K. J Therm Anal Calorim. 2015;121:975–81.

    CAS  Google Scholar 

  25. Usacheva TR, Pham Thi L, Sharnin VA. Calorimetric study of the molecular complex formation of glycyl–glycyl–glycine with 18-crown-6 in aqueous organic solvents. Russ J Gen Chem. 2017;87:591–9.

    CAS  Google Scholar 

  26. Chatjigakis AK, Donze C, Coleman AW. Solubility Behavior of β-Cyclodextrin In Water/cosolvent Mixtures. Anal Chem. 1992;64:1632–4.

    CAS  Google Scholar 

  27. Coleman AW, Munoz M, Chatjigakis AK. Classification of the solubility behaviour of β-cyclodextrin in aqueous-co-solvent mixtures. J Phys Org Chem. 1993;6:651–9.

    CAS  Google Scholar 

  28. Meshkov AN, Gamov GA. KEV: a free software for calculating the equilibrium composition and determining the equilibrium constants using UV–Vis and potentiometric data. Talanta. 2019;198:200–5.

    CAS  PubMed  Google Scholar 

  29. **ngen H, Ruisen L, Hanxing Z. Enthalpies and entropies of dissolution and dissociation of benzoic acid in EtOH-H2O and i-PrOH-EtOH-H2O mixtures. Acta Phys Chim Sinica. 1999;15:838–44.

    Google Scholar 

  30. Usacheva TR, Ledenkov SF, Sharnin VA. Complex formation of Ag+ with polyether 18-crown-6. Calorimetric and potentiometric methods. J Therm Anal Calorim. 2002;70:379–85.

    CAS  Google Scholar 

  31. Arnett EM, Bentrude WG, Burke JJ, MccDuggleby P. Solvent effects in organic chemistry. V. Molecules, ions, and transition states in aqueous–ethanol. J Amer Chem Soc. 1965;87:1541–52.

    CAS  Google Scholar 

  32. Afanasiev VN, Efremova LS, Volkova TV. Physical-chemical properties of binary solvents. Water-containing systems; Publisher: Academy of Sciences of the Union of Soviet Republics (USSR) Institute of non-aqueous solution chemistry. Russia. 1988; Part I, p. 104 (in Russian).

  33. Szejtli J. Introduction and general overview of cyclodextrin chemistry. Chem Rev. 1998;98:1743–53.

    CAS  PubMed  Google Scholar 

  34. Sifaoui H, Modarressi A, Magri P, Stachowicz-Kuśnierz A, Korchowiec J, Rogalski M. Formation of β-cyclodextrin complexes in an anhydrous environment. J Mol Model. 2016;22:207–20.

    PubMed  PubMed Central  Google Scholar 

  35. Price DM. Temperature calibration of differential scanning calorimeters. J Therm Anal. 1995;45:1285–96.

    CAS  Google Scholar 

  36. Sorum CH, Durand EA. The melting of binary eutectics. J Am Chem Soc. 1952;74:1071–3.

    CAS  Google Scholar 

  37. Murray JP, Cavell KJ, Hill JO. A DSC study of benzoic acid. A suggested calibrant compound. Thermochim Acta. 1980;36:97–101.

    CAS  Google Scholar 

  38. Kim KH, Frank MJ, Henderson NL. Application of differential scanning calorimetry to the study of solid drug dispersions. J Pharm Sci. 1985;74:283–9.

    CAS  PubMed  Google Scholar 

  39. Borodin VA, Vasilev VP, Kozlovskiy EA. Processing of results of calorimetric measurements on a computer when studying the complex equilibria in solutions. Zh Neorg Khim. 1982;27:2169–72 (in Russian).

    CAS  Google Scholar 

  40. Harata K. Induced circular dichroism of cycloamylose complexes with meta-and para-disubstituted benzenes. Bioorg Chem. 1981;10:255–65.

    CAS  Google Scholar 

  41. Lewis EA, Hansen LD. Thermodynamics of binding of guest molecules to α and β-cyclodextrins. J Chem Soc Perkin Trans. 1972;2:2081–5.

    Google Scholar 

  42. Krestov GA. Ionic solvation, Ellis Horwood Ed., New York-London-Toronto-Sydney-Tokyo-Singapore, 1994.

  43. Belica S, Sadowska M, Stepniak A, Graca A, Pałecz B. Enthalpy of solution of α- and β-cyclodextrin in water and in some organic solvents. J Chem Therm. 2014;69:112–7.

    CAS  Google Scholar 

  44. Usacheva TR, Sharnin VA. A thermodynamic study of reactions of amino acids with crown ethers in nonaqueous media as examples of guest-host molecular complex formation. Russ Chem Bull. 2015;64:2536–44.

    CAS  Google Scholar 

  45. Usacheva TR, Kabirov DN, Beregova DA, Gamov GA, Sharnin VA, Marco B, Laura M, Concetta G. Thermodynamics of complex formation between hydroxypropyl-β-cyclodextrin and quercetin in water-ethanol solvents at T = 298.15 K. J Therm Anal Calorim. 2019;138:417–24.

    CAS  Google Scholar 

Download references

Acknowledgements

This work was funded by Vietnam National Foundation for Science and Technology Development (NAFOSTED) under the Grant Number 104.06–2017.329 by RFBR and VAST according to the research project No. 19–53-54004 and by Ministry of Foreign Affairs and International Cooperation of Italy [grants in favor of foreign citizens not residing in Italy and Italian citizens living abroad, No. 946–22/10/2018]. ITC 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 authors thank the University of Naples Federico II for the financial support of their collaboration which contributed to the preparation of this paper.

Author information

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

    Tatyana Usacheva, Dzhovidon Kabirov, Diana Alister & Valentin Sharnin

  2. Institute for Tropical Technology, Vietnam Academy of Science and Technology, Hoang Quoc Viet str. 18, Cau Giay, Hanoi, Vietnam

    Thi Lan Pham, Tuan Dung Nguyen, Xuan Minh Vu & Thi My Hanh Le

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

    Concetta Giancola

Authors
  1. Tatyana Usacheva
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Thi Lan Pham
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tuan Dung Nguyen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Dzhovidon Kabirov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Diana Alister
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xuan Minh Vu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Thi My Hanh Le
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Valentin Sharnin
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Concetta Giancola
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Tatyana Usacheva or Thi Lan Pham.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Usacheva, T., Pham, T.L., Nguyen, T.D. et al. Host–guest inclusion complex of β-cyclodextrin and benzoic acid in water–ethanol solvents: spectroscopic and thermodynamic characterization of complex formation. J Therm Anal Calorim 142, 2015–2024 (2020). https://doi.org/10.1007/s10973-020-09807-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-020-09807-4

Keywords

Search

Navigation