Advertisement

Theoretica chimica acta

, Volume 54, Issue 1, pp 73–82 | Cite as

Quantum mechanical studies of environmental effects on biomolecules

IX. Structure and hydration of thiourea
  • Yoshimasa Orita
  • Akio Ando
  • Hiroshi Abe
  • Shin-ichi Yamabe
  • Hélène Berthod
  • Alberte Pullman
Original Investigations

Abstract

SCFab initio computations have been performed on the structure, molecular potential and hydration scheme of thiourea in view of a comparison with urea and more generally as a model of the conjugated S=CNH-group as compared to O=CNH-. In contrast to the carbonyl oxygen, both σ and π acceptor, the sulfur atom of the thiocarbonyl is a σ donor but a π acceptor and this results in an enhancement of the double-bond character of thiourea. The CN bond is less attractive for a proton than urea. The hydration scheme indicates a maximum number of four water molecules directly bound to thiourea.

Key words

Thiourea Conjugated thiocarbonyl Thioanalogs Hydration of thiocarbonyls 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Orita, Y., Pullman, A.: Theoret. Chim. Acta (Berl.)45, 257 (1977)CrossRefGoogle Scholar
  2. 2.
    Orita, Y., Pullman, A.: Theoret. Chim. Acta (Berl.)46, 251 (1977)CrossRefGoogle Scholar
  3. 3.
    Pullman, A., Alagona, G., Tomasi, J.: Theoret. Chim. Acta (Berl.)33, 87 (1974)CrossRefGoogle Scholar
  4. 4.
    Alagona, G., Pullman, A., Scrocco, E., Tomasi, J.: Intern. J. Peptide Protein Res.5, 251 (1973)Google Scholar
  5. 5.
    Pullman, A., Berthod, H., Giessner-Prettre, C., Hinton, J. F., Harpool, D.: J. Am. Chem. Soc.100, 3991 (1978)CrossRefGoogle Scholar
  6. 6.
    Rabinowitz, L.: Am. J. Physiol.209, 188 (1965)Google Scholar
  7. 7.
    Orita, Y., Urakabe, S., Shirai, D., Furakawa, T., Abe, H.: Jap. J. Nephrology7, 111 (1965)Google Scholar
  8. 8.
    Nishimura, S.: Progr. Nucleic Acid Res. Mol. Biol.12, 50, 1972Google Scholar
  9. 9.
    Barrell, B. G., Clark, B. F. C.: Handbook of nucleic acid sequences. Oxford: Joynson-Bruvvers 1974Google Scholar
  10. 10.
    Feldman, M. Ya.: Progr. Biophys. Mol. Biol.32, 83 (1977)Google Scholar
  11. 11.
    Elion, G. B., Hitchings, G. H.: Advan. Chemotherapy2, 91 (1965)Google Scholar
  12. 12.
    Roy Burman, P.: Analogs of nucleic acid components. New York: Springer Verlag 1970Google Scholar
  13. 13.
    Shefter, E., Mautner, H. G.: J. Am. Chem. Soc.89, 1249 (1967)Google Scholar
  14. 14.
    Saenger, W.: J. Am. Chem. Soc.94, 621 (1272)Google Scholar
  15. 15.
    Thewalt, U., Bugg, C. E.: J. Am. Chem. Soc.94, 8892 (1972)CrossRefGoogle Scholar
  16. 16.
    Hawkinson, S. W.: Acta Cryst.B33, 80 (1977)Google Scholar
  17. 17.
    Hitchings, G. H., Elion, G. B., in: The purines, theory and experiment, p. 565. Jerusalem Symposia on Quantum Chemistry and Biochemistry, Vol. IV, Bergmann, E., Pullman, B. Eds. New York: Academic Press 1972Google Scholar
  18. 18.
    Sundaralingam, M.: Ref. [17], 73Google Scholar
  19. 19.
    Bugg, C. E.: Ref. [17], 178Google Scholar
  20. 20.
    Siegbahn, R. F., Roos, B.: Theoret. Chim. Acta (Berl.)40, 47 (1975)Google Scholar
  21. 21.
    Truter, M. R.: Acta Cryst.22, 566 (1967). (The C2N3H5 angle was erroneously given as 114 ° against the correct value of 133 °; we thank Dr. Truter for kindly checking this point)CrossRefGoogle Scholar
  22. 22.
    Mulliken, R. S.: J. Chem. Phys.23, 1833 (1955)Google Scholar
  23. 23.
    Bonaccorsi, R., Scrocco, E., Tomasi, J.: J. Chem. Phys.52, 5270 (1970)CrossRefGoogle Scholar
  24. 24.
    McClellan, A. L.: Tables of experimental dipole moments. San Francisco: W. A. Freeman (1963)Google Scholar
  25. 25.
    Bernardi, F., Csizmadia, I. G., Schlegel, H. B., Wolfe, S.: Can. J. Chem.53, 1144 (1975)Google Scholar
  26. 26.
    Berthod, H., Pullman, A.: Compt. Rend. Ac. Sci. Paris262C, 76 (1966)Google Scholar
  27. 27.
    Krackov, M. H., Lee, C. M., Mautner, H. G.: J. Am. Chem. Soc.87, 892 (1965)CrossRefGoogle Scholar
  28. 28.
    Boys, S. F., in: Quantum theory of atoms, molecules and the solid state, p. 253. Löwdin, P. O. Ed. New York: Academic Press 1966Google Scholar
  29. 29.
    Peters, D., Sana, M.: Program Boyloc. Louvain La Neuve (1977), by courtesy of Prof. Leroy and Dr. PetersGoogle Scholar
  30. 30.
    Stewart, W. E., Siddall, T. H.: Chem. Rev.70, 517 (1970)CrossRefGoogle Scholar
  31. 31.
    Stewart, W. E., Siddall, T. H.: J. Phys. Chem.74, 2027 (1970)CrossRefGoogle Scholar
  32. 32.
    Mullen, D., Hellner, E.: Acta Cryst.B34, 2789 (1978)Google Scholar
  33. 33.
    Le Gall, L., Le Narkov, A., Laurausan, J., Saumagne, P.: Can. J. Chem.29A, 1805 (1973)Google Scholar
  34. 34.
    Kulevsky, N., Froehlich, P. M.: J. Am. Chem. Soc.89, 4839 (1967)CrossRefGoogle Scholar
  35. 35.
    Bonaccorsi, R., Pullman, A., Scrocco, E., Tomasi, J.: Chem. Phys. Letters12, 622 (1972)Google Scholar
  36. 36.
    Pullman, A., in: Chemical and biochemical reactivity, p. 1. The Jerusalem Symposia on Quantum Chemistry and Biochemistry, VI, Bergmann, E. D., Pullman, B. Eds. New York: Academic Press 1974Google Scholar
  37. 37.
    Gentric, D.: Thèse de Doctorat d'Etat, Université de Bretagne Occidentale 1979, and Refs. thereinGoogle Scholar
  38. 38.
    Wilson, M. S., McCloskey, J. A.: J. Am. Chem. Soc.97, 3436 (1975)Google Scholar
  39. 39.
    Meot-ner, M., Field, F. H.: J. Chem. Phys.66, 4527 (1977)Google Scholar
  40. 40.
    Hays, R. M., Harkness, S. H., Franki, N., in: Urea and the kidney, p. 149. Schmidt-Nielsen, B., Ed. Amsterdam: Excerpta Med. Found. 1970Google Scholar
  41. 41.
    Bugg, C. F., Thewalt, U.: Acta Cryst.B31, 121 (1975)Google Scholar
  42. 42.
    Gramstad, T., Sandstrom, J.: Spectrochim. Acta25A, 31 (1969)Google Scholar

Copyright information

© Springer-Verlag 1979

Authors and Affiliations

  • Yoshimasa Orita
    • 1
  • Akio Ando
    • 1
  • Hiroshi Abe
    • 1
  • Shin-ichi Yamabe
    • 2
  • Hélène Berthod
    • 3
  • Alberte Pullman
    • 3
  1. 1.Department of MedicineOsaka University Medical SchoolOsakaJapan
  2. 2.Department of ChemistryNara University of EducationNaraJapan
  3. 3.Institut de Biologie Physico-ChimiqueLaboratoire de Biochimie Théorique, associé au C.N.R.S.ParisFrance

Personalised recommendations