Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Molecular dynamics simulations on the protonated 222. H+ and 222.2H+ cryptands in water:Endo versusexo conformations

  • 54 Accesses

  • 21 Citations

Abstract

MD simulations on the 222 cryptand, monoprotonated 222.H+ and diprotonated 222.2H+ in theendo-endo andexo-exo conformations have been performedin vacuo and in a bath of water molecules. It is found that intrinsicallyendo protonation is favoured overexo protonation due to internal N-H+ ... O hydrogen bonding which makes the cage more rigid. On the other hand,endo protonated forms display ‘hydrophobic’ hydration compared toexo forms. For the monoprotonated 222. H+ endo conformer, one water molecule is hydrogen bonded inside the cage thereby forming a ‘water cryptate’. From the hydration pattern found previously for the neutral 222 cryptand and for its cation complexes, we suggest mechanisms (not involvingexo toendo conversions) for the protonation of 222 and for acid catalysed decomplexation of cryptates in theendo-endo form.

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

References

  1. 1.

    B. Dietrich, J. M. Lehn, J. P. Sauvage and J. Blanzat:Tetrahedron 29, 1629 (1973).

  2. 2.

    B. Dietrich, J. M. Lehn and J. P. Sauvage:Tetrahedron 29, 1647 (1973).

  3. 3.

    H. E. Simmons and C. H. Park:J. Am. Chem. Soc. 90, 2428 (1968).

  4. 4.

    J. M. Lehn:Struct. Bonding 161, 1 (1973).

  5. 5.

    M. Dobler inIonophores and their Structures., Editor (Eds), Wiley Interscience, New York, 1981.

  6. 6.

    B. Metz, D. Moras and R. Weiss:J. Chem. Soc., Perkin Trans. 2 423 (1976).

  7. 7.

    G. Wipff and P. A. Kollman:New. J. Chem. 9, 457 (1985).

  8. 8.

    R. Gene, S. H. Jacobson and R. Pizer:J. Am. Chem. Soc. 108, 1150 (1986).

  9. 9.

    G. Wipff and J. M. Wurtz inDynamic Views of Macrocyclic Receptors: Molecular Dynamics Simulations and Normal Modes Analysis, Pullman, R. (ed.), Reidel, Dordrecht, 1988, p. 1.

  10. 10.

    P. Auffinger and G. Wipff: ‘Hydration of the Bicylic 222 Cryptand and 222 Cryptates Studied by Molecular Dynamics Simulations’,J. Am. Chem. Soc., (1991).

  11. 11.

    B. Metz, D. Moras and R. Weiss:J. Chem. Soc, Chem. Commun. 444 (1971).

  12. 12.

    R. Pizer:J. Am. Chem. Soc. 100, 4239 (1978).

  13. 13.

    B. G. Cox, H. Schneider and J. Stroka:J. Am. Chem. Soc. 100, 4746 (1978).

  14. 14.

    B. G. Cox and H. Schneider:J. Chem. Soc., Perkin Trans. 2 1293 (1979).

  15. 15.

    A. M. Kjaer, P. E. Sorensen and J. Ulstrup:J. Chem. Soc., Chem. Commun. 965 (1979).

  16. 16.

    P. B. Smith, J. L. Dye, J. Cheney and J. M. Lehn:J. Am. Chem. Soc. 103, 6044 (1981).

  17. 17.

    B. G. Cox and H. Schneider:J. Am. Chem. Soc. 99, 2809 (1977).

  18. 18.

    B. G. Cox, D. Knop and H. Schneider:J. Phys. Chem. 84, 320 (1980).

  19. 19.

    E. L. Yee, O. A. Gansow and M. J. Weaver:J. Am. Chem. Soc. 102, 2278 (1980).

  20. 20.

    J. M. Bemtgen, M. E. Springer, V. M. Loyola, R. G. Wilkins and R. W. Taylor,Inorg. Chem. 23, 3348 (1984).

  21. 21.

    B. Dietrich, J. P. Kintzinger, J. M. Lehn, B. Metz and A. Zahidi,J. Phys. Chem. 91, 6600 (1987).

  22. 22.

    C. Singh, P. K. Weiner, J. Caldwell and P. A. Kollman;Amber 3.0, University of California, San Francisco (1987).

  23. 23.

    S. J. Weiner, P. A. Kollman, D. T. Nguyen and D. A. Case:J. Comput. Chem. 7, 230 (1986).

  24. 24.

    P. Auffinger and G. Wipff:J. Comput. Chem. 11, 19 (1990).

  25. 25.

    P. Grootenhuis, Personal communication (1988).

  26. 26.

    W. L. Jorgensen, J. Chandrasekhar and J. D. Madura:J. Chem. Phys. 79, 926 (1983).

  27. 27.

    J. P. Ryckaert, G. Ciccotti and H. J. C. Berendsen,J. Comput. Phys. 23, 327 (1977).

  28. 28.

    G. Wipff and J. M. Wurtz,MDNM: a Program to Display Molecular Dynamics or Normal Modes of Vibrations on the PS300. (1987).

  29. 29.

    W. F. van Gunsteren and H. J. C. Berendsen,Groningen Molecular Simulation (GROMOS) Library Manual Biomos, Groningen (1987).

  30. 30.

    P. Auffinger, Thése de Doctorat, Université Louis-Pasteur, Strasbourg (1991).

  31. 31.

    B. Owenson, R. D. MacElroy and A. Pohorille:J. Am. Chem. Soc. 110, 6992 (1988).

  32. 32.

    B. G. Cox, J. Murray-Rust, P. Murray-Rust, N. van Truong and H. Schneider,J. Chem. Soc., Chem. Commun. 377 (1982).

  33. 33.

    H. J. Brügge, D. Carboo, K. von Deuten, A. Knöchel, J. Kopf and W. Dreissig,J. Am. Chem. Soc. 108, 107 (1986).

  34. 34.

    T. P. Straatsma and J. A. McCammon,J. Chem. Phys. 91, 3631 (1989).

  35. 35.

    G. R. Newcome, V. Majestic, F. Fronczek and J. L. Atwood,J. Am. Chem. Soc. 101, 1047 (1979).

  36. 36.

    S. Boudon and G. Wipff:J. Comput. Chem. 12, 42 (1990).

  37. 37.

    T. P. Lybrand, J. A. McCammon and G. Wipff,Proc. Natl. Acad. Sci. USA 83, 833 (1989).

  38. 38.

    J. V. van Eerden, S. Harkema and D. Feil,J. Phys. Chem. 92, 5076 (1988).

  39. 39.

    J. van Eerden, W. J. Briels, S. Harkema and D. Feil:Chem. Phys. Lett. 164, 370 (1989).

  40. 40.

    P. D. J. Grootenhuis and P. A. Kollman,J. Am. Chem. Soc. 111, 2152 (1989).

  41. 41.

    W. L. Jorgensen:Acc. Chem. Res. 22, 184 (1989).

  42. 42.

    M. H. Mazor, J. A. McCammon and T. P. Lybrand:J. Am. Chem. Soc. 112, 4411 (1990).

  43. 43.

    L. X. Dang and P. A. Kollman:J. Am. Chem. Soc. 112, 5716 (1990).

  44. 44.

    W. F. van Gunsteren inOn Testing Theoretical Models by Comparison of Calculated with Experimental Data., J. L. Rivail (Ed), Elsevier, Amsterdam, 1990, pp. 436.

  45. 45.

    P. D. J. Grootenhuis, P. A. Kollman, T. Malliavin and G. Wipff: Unpublished Results (1989).

  46. 46.

    P. D. J. Grootenhuis, P. A. Kollman, L. C. Groenen, D. N. Reinhoudt, G. J. van Hummel, F. Ugozzoli and G. D. Andreetti:J. Am. Chem. Soc. 112, 4165 (1990).

  47. 47.

    E. Kauffmann, J. M. Lehn and J. P. Sauvage:Helv. Chim, Acta 59, 1099 (1976).

  48. 48.

    G. Wipff and J. M. Wurtz:New. J. Chem. 13, 807 (1989).

  49. 49.

    P. D. J. Grootenhuis, J. W. H. M. Uiterwijk, D. N. Reinhoudt, C. J. van Staveren, E. J. R. Sudhölter, M. Bos, J. van Eerden, W. T. Klooster, L. Kruise and S. Harkema:J. Am. Chem. Soc. 108, 780 (1986).

  50. 50.

    C. J. van Staveren, V. M. L. J. Aarts, P. D. J. Grootenhuis, W. J. H. Droppers, J. van Eerden, S. Harkema and D. N. Reinhoudt:J. Am. Chem. Soc. 110, 8134 (1988).

  51. 51.

    I. Goldberg,Acta Crystallogr. B34, 3387 (1978).

  52. 52.

    F. Vögtle, W. M. Müller and W. H. Watson,Top. Curr. Chem. 125, 131 (1984).

  53. 53.

    D. N. Reinhoudt:J. Coord. Chem. 18, 21 (1988).

  54. 54.

    P. Groth,Acta Chem. Scand. A36, 109 (1982).

  55. 55.

    J. M. Lehn:Pure Appl. Chem. 50, 871 (1978).

  56. 56.

    J. P. Kintzinger: Personal communication (1990).

  57. 57.

    F. Arnaud-Neu, B. Spiess and M. J. Schwing-Weill,J. Chem. Res. (S) 10 (1982).

  58. 58.

    N. Morel-Desrosiers and J. P. Morel,J. Phys. Chem. 88, 1023 (1984).

  59. 59.

    R. M. Izatt, J. S. Bradshaw, S. A. Nielsen, J. D. Lamb, J. J. Christensen and D. Sen,Chem. Rev. 85, 271 (1985).

  60. 60.

    The authors are grateful to one of the referees who pointed out his earlier proposal.

  61. 61.

    D. J. Cram:Science 240, 760 (1988).

  62. 62.

    J. M. Lehn:Angew. Chem., Int. Ed. Engl. 27, 89 (1988).

  63. 63.

    G. Ranghino, S. Romano, J. M. Lehn and G. Wipff:J. Am. Chem. Soc. 107, 7873 (1985).

  64. 64.

    H. Matsuura, K. Fukuhara, K. Ikeda and M. Tachikake,J. Chem. Soc., Chem. Commun. 1814 (1989).

  65. 65.

    S. Boudon and G. Wipff: ‘How Important is Water in the Preoganization of Polyammonium Host Molecules’, inAdvances in Biomolecular Simulations, Troyanovski (ed.) 0000, (1991). G. Wipff: ‘Molecular Modeling Studies on Molecular Recognition: Crown Ethers, Cryptands and Cryptates. From Static Models in vacuo to Dynamical Models in Solution’J. Coord. Chem. B (1991).

Download references

Author information

Correspondence to G. Wipff.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Auffinger, P., Wipff, G. Molecular dynamics simulations on the protonated 222. H+ and 222.2H+ cryptands in water:Endo versusexo conformations. J Incl Phenom Macrocycl Chem 11, 71–88 (1991). https://doi.org/10.1007/BF01073686

Download citation

Key words

  • Cryptands
  • recognition
  • protonation
  • molecular dynamics
  • solvation
  • molecular modelling