Skip to main content
SpringerLink
Log in

Calix[4]azacrowns as ionophores for liquid–liquid extraction and facilitated transport of biological supramolecular complexes

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

The native and methyl ester amino acids have been extracted by calix[4]azacrowns 1 (1,3-[ethylene-bis-aminocarbonylmethoxy)]-p-tert-butylcalix[4]arene) and 2 (1,3-[propylene-bis-aminocarbonylmethoxy)]-p-tert-butyl-calix[4]arene) from an aqueous phase into a chloroform phase and transported through a chloroform liquid membrane as ion pairs in the presence of picrate or tropaeolin 00 as counter ions aiming their separation. The amino acids under study exhibited good extractability by calix[4]azacrowns 1 and 2. Both receptors 1 and 2 showed good extractability towards amino acids under study. The results are discussed in term of correlation of structural properties of amino acids and calix[4]azacrowns involved in experiments. In this respect, the influence of chain length of receptors upon extraction and transport of amino acids, and the nature of anions used as counter ions are evaluated.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Chart 1
Chart 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Lehn, J.-M.: Supramolecular Chemistry: Concepts and Perspective. Wiley-VCH, Weinheim (1995)

    Book  Google Scholar 

  2. Gutsche, C.D.: Calixarenes Revisited. The Royal Society of Chemistry, Cambridge (1998)

    Google Scholar 

  3. Vicens, J., Böhmer, V.: Calixarenes: A Versatile Class of Macrocyclic Compounds. Kluwer Academic Publishers, Dordrecht (1991)

    Google Scholar 

  4. Mutihac, L., Lee, J.H., Kim, J.S., Vicens, J.: Recognition of amino acids by functionalized calixarenes. Chem. Soc. Rev. (2011). doi:10.1039/c0cs00005a (on-line)

  5. Vicens, J., Harrowfield, J. (eds.): Calixarene in the Nanoworld. Springer, Dordrecht (2007)

    Google Scholar 

  6. Buschmann, H.-J., Mutihac, L.: Complexation, liquid-liquid extraction, and transport through a liquid membrane of protonated peptides using crown ethers. Anal. Chim. Acta 466, 101–108 (2002)

    Article  CAS  Google Scholar 

  7. Dondoni, A., Marra, A.: Calixarene and calixresorcarene glycosides: their synthesis and biological applications. Chem. Rev. 110, 4949–4977 (2010)

    Article  CAS  Google Scholar 

  8. Mokhtari, B., Pourabdollah, K., Dalali, N.: Analytical applications of calixarenes from 2005 up-to-date. J. Incl. Phenom. Macrocycl. Chem. 69, 1–55 (2011)

    Article  CAS  Google Scholar 

  9. Coleman, A.W., Perret, F., Mousa, A., Dupin, M., Guo, Y., Perron, H.: Calix[n]arenes as protein sensors. Top. Curr. Chem. 277, 31–88 (2007)

    Article  CAS  Google Scholar 

  10. Buschmann, H.-J., Mutihac, R.-C., Schollmeyer, E.: Complex formation of crown ethers and cryptands with alkali metal and ammonium ions in chloroform. J. Solution Chem. 38, 209–217 (2009)

    Article  CAS  Google Scholar 

  11. Böhmer, V.: Calixarenes, macrocycles with (almost) unlimited possibilities. Angew. Chem. Int. Ed. Engl. 34, 713–745 (1995)

    Article  Google Scholar 

  12. Mutihac, R., Cicuttin, A., Mutihac, R.-C.: Entropic approach to information coding in DNA molecules. Mat. Sci. Eng. 18, 51–60 (2001)

    Article  Google Scholar 

  13. Chen, C.-F.: Novel triptycene-derived hosts: synthesis and their applications in supramolecular chemistry. Chem. Commun. 47, 1674–1688 (2011)

    Article  CAS  Google Scholar 

  14. Buschmann, H.-J., Mutihac, L., Mutihac, R.-C., Schollmeyer, E.: Complexation behavior of cucurbit[6]uril with short polipeptides. Thermochim. Acta 430, 79–82 (2005)

    Article  CAS  Google Scholar 

  15. Sansone, F., Baldini, L., Casnati, A., Ungaro, R.: Calixarenes: from biomimetic receptors to multivalent ligands for biomolecular recognition. New J. Chem. 34, 2715–2728 (2010)

    Article  CAS  Google Scholar 

  16. Mutihac, L.: Functionalized calix[n]arenes as membrane transporters for biological compounds. A minireview. Curr. Drug. Discov. Technol. 5, 98–104 (2008)

    Article  CAS  Google Scholar 

  17. Buschmann, H.-J., Schollmeyer, E., Wenz, G., Mutihac, L.: Solvent influence upon complex formation between crown ethers and unprotonated amines. Thermochim. Acta 261, 1–5 (1995)

    Article  CAS  Google Scholar 

  18. Fyles, T.M.: Synthetic ion channels in bilayer membrane. Chem. Soc. Rev. 36, 335–347 (2007)

    Article  CAS  Google Scholar 

  19. Iqbal, K.S.J., Cragg, P.J.: Transmembrane ion transport by calixarenes and their derivatives. Dalton Trans. 1, 26–32 (2007)

    Article  Google Scholar 

  20. Cao, D., Kou, Y., Liang, J., Chen, Z., Wang, L., Meier, H.: A facile and efficient preparation of pillararenes and a pillarquinone. Angew. Chem. Int. Ed. 48, 9721–9723 (2009)

    CAS  Google Scholar 

  21. Kim, J.S., Quang, D.T.: Calixarene-derived fuorescent probes. Chem. Rev. 107, 3780–3799 (2007)

    Article  CAS  Google Scholar 

  22. Alfieri C, Dradi E, Pochini A, Ungaro R, Andreetti GD (1983) Synthesis, and X-ray crystal and molecular structure of a novel macro-bicyclic ligand:crowned p-t-butyl-calix[4]arene. J Chem Soc Chem Commun 1075–1077)

  23. Casnati, A., Pochini, A., Ungaro, R., Ugozzoli, F., Arnaud-New, F., Fanni, S., Schwing-Weill, M.-J., Egberlink, R.J.M., de Jong, F., Reinhoudt, D.N.: Synthesis, complexation, and membrane transport studies of 1,3-alternate calix[4]arene-crown-6 conformers: a new class of cesium selective. J. Am. Chem. Soc. 117, 2767–2777 (1995)

    Article  CAS  Google Scholar 

  24. Asfari, Z., Wenger, S., Vicens, J.: Calixcrowns and related molecules. Pure Appl. Chem. 67, 1037–1043 (1995)

    Article  CAS  Google Scholar 

  25. Ostaszewski, R., Stevens, T.W., Verboom, W., Reinhoudt, D.N., Kaspersen, F.M.: Calix(aza-)-crowns as potential ionophores for divalent and trivalent cations. Recl. Trav. Chim. Pays-Bas 110, 294–298 (1991)

    Article  CAS  Google Scholar 

  26. Oueslati, I.: Calix(aza)crowns: synthesis, recognition, and coordination. A mini review. Tetrahedron 63, 10840–10851 (2007)

    Article  CAS  Google Scholar 

  27. Abidi, R., Oueslati, I., Amri, H., Thuery, P., Nierlich, M., Asfari, Z., Vicens, J.: Synthesis, structure and complexing properties of new calix[4](aza)crowns. Tetrahedron Lett. 42, 1685–1689 (2001)

    Article  CAS  Google Scholar 

  28. Oueslati, I., Thuéry, P., Shkurenko, O., Suwinska, K., Harrowfield, J., Abidi, R., Vicens, J.: Calix[4]azacrowns: self-assembly and effect of chain length and O-alkylation on their metal ion-binding properties. Tetrahedron 63, 62–70 (2007)

    Article  CAS  Google Scholar 

  29. Kim, J.S., Son, O.J., Ko, J.W., Cho, M.H., Yu, I.Y., Vicens, J.: Synthesis and metal ion complexation studies of proton-ionizable calix[4]azacrown ethers in the 1,3-alternate conformation. J. Org. Chem. 65, 2386–2392 (2000)

    Article  CAS  Google Scholar 

  30. Danylyuk, O., Suwinska, K.: Solid-state interactions of calixarenes with biorelevant molecules. Chem. Commun. 5799–5813 (2009)

  31. Mutihac, L., Buschmann, H.-J., Tudorescu, A., Mutihac, R.: Some aspect of extractability and trasport of amino acid esters by calixarenes. J. Incl. Phenom. Macrocycl. Chem. 47, 123–128 (2003)

    Article  CAS  Google Scholar 

  32. Douteau-Guevel, N., Perret, F., Coleman, A.W., Morel, J.-P., Morel-Desrosiers, N.: Binding of dipeptides and tripeptides containing lysine or arginine by p-sulfonatocalixarenes in water: NMR and microcalorimetric studies. J. Chem. Soc. Perkin Trans. 2, 524–532 (2002)

    Google Scholar 

  33. Demirtas, H.N., Bozkurt, S., Durmaz, M., Yilmaz, M., Sirit, A.: Chiral calix[4]azacrowns for enantiomeric recognition of amino acid derivatives. Tetrahedron 65, 3014–3018 (2009)

    Article  CAS  Google Scholar 

  34. Kim, L., Hamdi, A., Stancu, A.D., Souane, R., Mutihac, L., Vicens, J.: Selective membrane transport of aminoa cids by functionalized calix[4]arenes. J. Incl. Phenom. Macrocycl. Chem. 66, 55–59 (2010)

    Article  CAS  Google Scholar 

  35. Hamdi, A., Souane, R., Kim, L., Mutihac, L., Vicens, J.: Extraction behaviour of amino acid esters by functionalised calix[4]arenes. J. Incl. Phenom. Macrocycl. Chem. 64, 95–100 (2009)

    Article  CAS  Google Scholar 

  36. Marcus, Y.: Ion Solvation. Wiley, Chichester (1985)

    Google Scholar 

  37. Pedersen, C.J.: Ionic complexes of macrocyclic polyethers. J. Fed. Proc. Fed. Am. Soc. Exp. Biol. 27, 1305–1309 (1968)

    CAS  Google Scholar 

  38. Tayar, N.El., Tsai, R.S., Carrupt, P.A., Testa, B.: Octan-1-ol-water partition coefficients of zwitterionic a-amino acids. Determination by centrifugal partition chromatography and factorization into steric/hydrophobic and polar components. J. Chem. Soc., Perkin Trans. 2, 79–84 (1992)

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Analytical Chemistry, University of Bucharest, 4-12 Regina Elisabeta Blvd., Bucharest, 030018, Romania

    Ioana Varduca Enache & Lucia Mutihac

  2. IPHC-ULP-ECPM-CNRS, 25, rue Becquerel, 67087, Strasbourg, France

    Amel Ben Othman & Jacques Vicens

Authors
  1. Ioana Varduca Enache
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lucia Mutihac
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Amel Ben Othman
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jacques Vicens
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Lucia Mutihac or Jacques Vicens.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Enache, I.V., Mutihac, L., Othman, A.B. et al. Calix[4]azacrowns as ionophores for liquid–liquid extraction and facilitated transport of biological supramolecular complexes. J Incl Phenom Macrocycl Chem 71, 537–543 (2011). https://doi.org/10.1007/s10847-011-9944-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-011-9944-3

Keywords

Search

Navigation