Science in China Series B: Chemistry

, Volume 47, Issue 1, pp 24–33 | Cite as

Systematic study of the transfer of amino acids across the water/l,2-dichloroethane interface facilitated by dibenzo-18-crown-6

  • Yong Chen
  • Yi Yuan
  • Meiqin Zhang
  • Fei Li
  • Peng Sun
  • Zhao Gao
  • Yuanhua Shao
Article

Abstract

Failitated ion transfer reactions of 20 amino acids with dibenzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, lle, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (β°), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively. The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization. Moreover, the association constants and the standard rate constants for different amino acids showed good correlations with their hydrophobicity ), except Gly and Met, which inferred that the selectivity of such heterogeneous complex reaction for different amino acids with DB18C6, was not only affected by discrimination in binding these ions to the crown ether macro-cycle, but also significantly modified by the ion transfer Gibbs energy which was closely related to the structure of the transferred ions, protonated amino acids.

Keywords

inicro-/nano-pipet water/1,2- dichloroethane interface facilitated ion transfer cyclic voltammetry amino acid 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Stephen, M. T., Eric, J. T., Alvin, L. C., Microcalorimetric determination of thermodynamic parameters for ionophore-siderophore host-guest complex formation, Inorg. Chem., 2000, 39: 1071–1075.CrossRefGoogle Scholar
  2. 2.
    Koryta, I., Electrochemical polarization phenomena at the interface of two immiscible electrolyte solutions, Electrochim. Acta, 1979,24:293–300.CrossRefGoogle Scholar
  3. 3.
    Girault, H. H., Charge transfer across liquid-liquid interface, in Modern Aspect of Electrochemistry (eds. Bockris, J. O’M., Con- way, B. E., White, R. E.), New York: Plenum Press, 1993, 1.Google Scholar
  4. 4.
    Taylor, G., Girault, H. H., Ion transfer reactions across a liquid-liquid interface supported on a micropipette tip, J. Electroanal. Chem., 1986, 208:179–183.CrossRefGoogle Scholar
  5. 5.
    Beattie, P. D., Delay, A., Girault, H. H., Investigation of the kinetics of assisted potassium ion transfer by dibenzo-18-crown-6 at the micro-ITIES by means of steady-state voltammetry, J. Electroanal. Chem., 1995, 380: 167–175.CrossRefGoogle Scholar
  6. 6.
    Su, B., Shao, Y. H., Mechanism of sodium and potassium ions transfer facilitated by dibenzo-15-crown-5 across the water/1,2-dichloroethane interface using micropipettes, Chinese Science Bulletin, 2002, 47(16): 1325–1329.CrossRefGoogle Scholar
  7. 7.
    Stewart, A. A., Shao, Y., Pereira, C. M. et al., Micropipettes as a tool for the determination of the ionic species limiting the potential window at liquid/liquid interfaces, J. Electroanal. Chem., 1991, 305: 135–139.CrossRefGoogle Scholar
  8. 8.
    Yatziv, Y., Turyan, I., Mandler, D., A new approach to micropatterning: application of potential-assisted ion transfer at the liquid-liquid interface for the local metal deposition, J. Am. Chem. Soc., 2002, 124:5618–5619.CrossRefGoogle Scholar
  9. 9.
    Shao, Y., Mirkin, M. V., Fast kinetic measurements with nanome ter-sized pipets, Transfer of potassium ion from water into dichloroethane facilitated by dibenzo-18-crown-6, J. Am. Chem. Soc., 1997, 119(34): 8103–8104.CrossRefGoogle Scholar
  10. 10.
    Yuan, Y., Shao, Y., Systematic investigation of alkali metal ion transfer across the micro- and nano-water/1, 2-dichloroethane interfaces facilitated by dibenzo-18-crown-6, J. Phys. Chem. B., 2002, 106: 7809–7814.CrossRefGoogle Scholar
  11. 11.
    Dvorak, O., Mareck, V., Semec, Z., Selective complexation of biogenic amines by macrobyclic polyethers at a liquid/liquid interface, J. Electroanal. Chem., 1991, 300: 407–113.CrossRefGoogle Scholar
  12. 12.
    Sawada, S., Osakai, T., Hydroph obi city of oligopeptides: a voltammetric study of the transfer of dipeptides facilitated by dibenzo-18-crown-6 at the nitrobenzene/water interface, Phys. Chem. Chem. Phys., 1999, 1: 4819–1825.CrossRefGoogle Scholar
  13. 13.
    Jack, K., Russell, F. D., A simple method for displaying the hydropathic character of a protein, J. Mol. Biol., 1982, 157:105–132.CrossRefGoogle Scholar
  14. 14.
    Matasuda, H., Yamada, Y., Kanamori, K. et al., On the facilitation effect of neutral macrocyclic ligands on the ion transfer across the interface between aqueous and organic solution, I. Theoretical equation of ion-transfer-polarographic current-potential curves and its experimental verification, Bull. Chem. Soc. Jpn., 1991, 64: 1497–1508.CrossRefGoogle Scholar
  15. 15.
    Shao, Y., Steawart, A. A., Girault, H. H., Determination of the half-wave potential of the species limiting the potential window, J. Chem. Soc. Faraday Trans., 1991, 87: 2593–2597.CrossRefGoogle Scholar
  16. 16.
    Lee, H. J., Beriet, G., Girault, H. H., Amperometric detection of alkali metal ions on micro-fabricated composite polymer membranes, J. Electroanal. Chem., 1998,453: 211–219.CrossRefGoogle Scholar
  17. 17.
    Akamatsu, M., Yoshida, Y., Nakamura, H. et al., Hydrophobicity of di- and tripeptides having unionizable side chains and correlation with substituent parameters, Quant. Struct. -Acta Relat, 1989, 9: 195–203.CrossRefGoogle Scholar
  18. 18.
    Reymond, F., Chopineaux, C. Y., Steyaert, G. et al., Ionic partition diagrams of ionisable drugs: pH-lipophilicity profiles, transfer mechanisms and charge effects on solvation, J. Electroanal. Chem., 1999,462: 235–250.CrossRefGoogle Scholar
  19. 19.
    Shao, Y., Osborne, M. D., Girault, H. H., Assisted ion transfer at the micro-ITIES supported at the tip of micropipettes, J. Electroanal. Chem., 1991, 318: 101–109.CrossRefGoogle Scholar
  20. 20.
    Timko, J. M., Moore, S. S., Walba, D. M. et al., Host-gest complexation, 2. Structural units that control association constants between polyethers and tert-butylammonium salts, J. Am. Chem. Soc., 1977, 99:4207–1219.CrossRefGoogle Scholar
  21. 21.
    Behr, J. P., Lehn, J. M., Vierling, P., Molecular receptors, Structure effects and substrate recognition in binding of organic and biogenic ammonium ions by chiral polyfunctional macrocyclic polyethers bearing amino-acid and other side-chains, Helvetic. Chimica. Acta, 1982, 65: 1853–1867.CrossRefGoogle Scholar
  22. 22.
    Mirkin, M. V., Bard, A. J., Simple analysis of quasi-reversible steady-state voltammograms, Anal. Chem., 1992, 64: 2293 - 2302.CrossRefGoogle Scholar

Copyright information

© Science in China Press 2004

Authors and Affiliations

  • Yong Chen
    • 1
  • Yi Yuan
    • 1
  • Meiqin Zhang
    • 1
  • Fei Li
    • 1
  • Peng Sun
    • 1
  • Zhao Gao
    • 1
  • Yuanhua Shao
    • 1
    • 2
  1. 1.State Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchunChina
  2. 2.College of Chemistry and Molecular EngineeringPeking UniversityBeijingChina

Personalised recommendations