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Determination of binding constants of various alkali metal cations with p-sulfonatocalix[8]arene by using inclusion equilibrium with thionine dye

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Abstract

The binding constants of various alkali metal cations with water-soluble p-sulfonatocalix[8]arene (Calix-S8) were determined spectrophotometrically by using the inclusion equilibrium of thionine (Th) dye as a chemical indicator. Depending on the kind of alkali metal cations, the inclusion constants of Calix-S8 for Th decrease steeply with an increase in salt concentrations. Alkali metal cations compete with the organic guest Th in the Calix-S8 inclusion. Based on a competitive binding experiment, the binding constants of alkali metal cations with Calix-S8 were evaluated to be 17, 60, and 11 dm6 mol−2 for Na+, K+, and Cs+, respectively. We have demonstrated an absorption-based method of evaluating the binding constants of spectroscopically inert metal cations with Calix-S8 and shown the effects of salts on the molecular recognition of Calix-S8.

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References

  1. Schneider, H.-J., Gutes, D., Scheider, U.: A macrobicyclic polyphenoxide as receptor analogue for choline and related ammonium compounds. Angew. Int. Ed. Engl. 25, 647–649 (1986)

    Article  Google Scholar 

  2. Ikeda, A., Shinkai, S.: Novel cavity design using calix[n]arene skeletons: toward molecular recognition and metal binding. Chem. Rev. 97, 1713–1734 (1997) (references therein)

    Google Scholar 

  3. Dsouza, N., Pischel, U., Nau, W.M.: Fluorescent dyes and their supramolecular host/guest complexes with macrocycles in aqueous solution. Chem. Rev. 111, 7941–7980 (2011)

    Article  CAS  Google Scholar 

  4. Shinkai, S., Mori, S., Tsubaki, T., Sone, T., Manabe, O.: New water-soluble host molecules derived from calix[6]arene. Tetrahedron Lett. 25, 5315–5318 (1984)

    Article  CAS  Google Scholar 

  5. Guo, D.-S., Wang, K., Liu, Y.: Selective binding behaviors of p-sulfonatocalixarenes in aqueous solution. J. Incl. Phenom. Macrocycl. Chem. 62, 1–21 (2008)

    Article  CAS  Google Scholar 

  6. Oshita, K., Tkayanagi, T., Oshima, M., Motomizu, S.: Complex formation analysis of water-soluble calixarenes by capillary zone electrophoresis. J. Chromatogr. A 934, 113–122 (2001)

    Article  CAS  Google Scholar 

  7. Thuery, P., Masci, B.: Synthesis and crystal structure of 1:2 mixed uranyl/alkali metal ions (Li+, Na+, K+, Cs+) complexes of p-tert-butyl-tetrahomodioxacalix[4]arene. Dalton Trans. 2411–2417 (2003)

  8. Meier, U.C., Detellier, C.: Complexation of the sodium cation by a calix[8]arene derivative: formation of 2:1 and 3:1 Na+-calixarene complexes in solution. Supramol. Chem. 9, 289–295 (1998)

    Article  CAS  Google Scholar 

  9. Tomisic, V., Galic, N., Bertosa, B., Frkanec, L., Simeon, V., Zinic, M.: Hydrogen bonding and solvent effects on complexation of alkali metal cations by lower rim calix[4]arene tetra(O-[N-acetyl-d-phenylglycine methyl ester]). J. Incl. Phenom. Macrocycl. Chem. 53, 263–268 (2005)

    Article  CAS  Google Scholar 

  10. Arnaud-Neu, F., Collins, E.M., Deasy, M., Ferguson, G., Harris, S.J., Kaitner, B., Lough, A.J., Mckervey, M.A., Marques, E., Ruhl, B.L., Schwing-Weill, M.J., Seward, E.M.: Synthesis. X-ray crystal structures and cation-binding properties of alkyl calixaryl esters and ketones, a new family of macrocyclic molecular receptors. J. Am. Chem. Soc. 111, 8681–8691 (1989)

    Article  CAS  Google Scholar 

  11. Bakirci, H., Koner, A.L., Nau, W.M.: Binding of inorganic cations by p-sulfonatocalix[4]arene monitored through competitive fluorophore displacement in aqueous solution. Chem. Commun. 5411–5413 (2005)

  12. Basilio, N., Garcia-Rio, L., Martin-Pastor, M.: Counterion binding in solutions of p-sulfonatocalix[4]arene. J. Phys. Chem. B 114, 7201–7206 (2010)

    Article  CAS  Google Scholar 

  13. Scott, R.L.: Some comments on the Benesi–Hildebrand equation. Recueil des Travaux Chimiques des Pays-Bas et de la Belgique 75, 787–789 (1956)

    CAS  Google Scholar 

  14. Sueishi, Y., Inazumi, N., Hanaya, T.: Effects of pressure on inclusion complexation of methylene blue with water-soluble p-sulfonatocalix[n]arenes. J. Phys. Org. Chem. 18, 448–455 (2005)

    Article  CAS  Google Scholar 

  15. Sueishi, Y., Asano, K.: Effects of external pressure and solvent polarity on inclusion complexations of phenothiazine and trans-4-[4-(dimethylamino)styryl]-1-methylpyridinium with water-soluble p-sulfonatocalix[8]arene in alcohol–water mixtures. J. Incl. Macrocycl. Chem. 63, 37–42 (2009)

    Article  CAS  Google Scholar 

  16. Silwa, W., Girek, T.: Calixarene complexes with metal ions. J. Incl. Macrocycl. Chem. 66, 15–41 (2010)

    Article  Google Scholar 

  17. Morel, J.-P., Morel-Desrosiers, N.: Binding of monovalent metal cations by the p-sulfonatocalix[4]arene: experimental evidence for cation–π interactions in water. Org. Biomol. Chem. 4, 462–465 (2006)

    Article  CAS  Google Scholar 

  18. Guo, D.-S., Uzunova, V.D., Su, X., Liu, Y., Nau, W.M.: Operational calixarene-based fluorescent sensing systems for choline and acetylcoline and their application to enzymatic reactions. Chem. Sci. 2, 1722–1734 (2011)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama, 700-8530, Japan

    Yoshimi Sueishi & Hiroe Mori

  2. Technical Support Division, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka, 560-0043, Japan

    Naoya Inazumi

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  1. Yoshimi Sueishi
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  2. Hiroe Mori
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  3. Naoya Inazumi
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Correspondence to Yoshimi Sueishi.

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Sueishi, Y., Mori, H. & Inazumi, N. Determination of binding constants of various alkali metal cations with p-sulfonatocalix[8]arene by using inclusion equilibrium with thionine dye. J Incl Phenom Macrocycl Chem 75, 235–238 (2013). https://doi.org/10.1007/s10847-012-0202-0

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