View PDF Version
 
DOI: 10.1039/A708564H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 1687-1692

Kinetics of interaction of the thione unit in 4-thio-2′-deoxyuridine and 4-thiouridine 5′-monophosphate with rapidly reacting gold(III) complexes[hair space]‡

(Note: The full text of this document is currently only available in the PDF Version )

Anna Ericson, John C. Arthur, Robert S. Coleman, Lars I. Elding and Sofi K. C. Elmroth

Abstract

Reactions of 4-thio-2′-deoxyuridine d(s4U) and 4-thiouridine 5′-monophosphate s4UMP with trans-[AuY2Cl2]+/– (Y = CN– or NH3) have been investigated by conventional and high-pressure stopped-flow spectrophotometry in aqueous solution with 2.9 ⩽ pH ⩽ 7.0. For a given combination of metal complex and sulfur donor the observed second-order rate constants decreased with increasing pH. In the pH range 2.9 to 5.5 this decrease is mainly due to displacement of the pH-dependent equilibrium trans-[AuY2Cl2]+/–[hair space][hair space]+[hair space][hair space]H2O[hair space][hair space]⇌[hair space][hair space]trans-[AuY2Cl(OH)]+/–[hair space][hair space]+[hair space][hair space]Cl–[hair space][hair space]+[hair space][hair space]H+ and formation of an increasing fraction of the less reactive gold(III) hydroxo complex. The activation parameters ΔH[hair space] ‡, ΔS[hair space] ‡ and ΔV[hair space] ‡ at pH 4.0 for substitution of chloride for thione at trans-[AuY2Cl2]+/– indicate an associative interchange process. When the thione-containing nucleotide reacts with the cation, steric and electrostatic interactions between the metal complex and the phosphate group oppose each other and the rate of the reaction of trans-[Au(NH3)2Cl2]+ with s4UMP is approximately the same as with d(s4U). Thus, the electrostatic outer-sphere interaction with a single phosphate group adjacent to the kinetically preferred binding site is not sufficient to induce a reactivity that significantly exceeds that of direct interaction between the thione and the rapidly reacting gold(III) centre. In contrast, reaction of trans-[Au(CN)2Cl2]– with s4UMP is significantly slower than with d(s4U), most likely due to the combined effect of electrostatic repulsion and steric blocking.

References

  1. W. Saenger, Principles of nucleic acid structure, Springer, New York, 1st edn., 1984 Search PubMed.
  2. G. A. Neyhart, W. A. Kalsbeck, T. W. Welch, N. Grover and H. H. Thorp, in Mechanistic Bioinorganic Chemistry, eds. H. H. Thorp and V. L. Pecoraro, American Chemical Society, Denver, CO, 1995, pp. 405–430 Search PubMed.
  3. J. K. Barton, in Bioinorganic Chemistry, eds. I. Bertini, H. B. Gray, S. J. Lippard and J. Valentine, University Science Books, Mill Valley, CA, 1994, pp. 455–504 Search PubMed.
  4. J. P. Whitehead and S. J. Lippard, in Interactions of Metal Ions with Nucleotides, Nucleic Acids and Their Constituents, eds. A. Siegel and H. Siegel, Marcel Dekker, New York, 1996, vol. 32, pp. 687–726 Search PubMed.
  5. S. K. C. Elmroth and S. J. Lippard, J. Am. Chem. Soc., 1994, 116, 3633 CrossRef CAS.
  6. S. K. C. Elmroth and S. J. Lippard, Inorg. Chem., 1995, 34, 5234 CrossRef CAS.
  7. W. I. Sundquist, D. P. Bancroft, L. Chassot and S. J. Lippard, J. Am. Chem. Soc., 1988, 110, 8559 CrossRef CAS.
  8. J.-M. Malinge, M. Sip, A. J. Blacker, J.-M. Lehn and M. Leng, Nucleic Acids Res., 1990, 18, 3887 CAS.
  9. U. Hänsler and S. E. Rokita, J. Am. Chem. Soc., 1993, 115, 8554 CrossRef CAS.
  10. J. Kjellström and S. K. C. Elmroth, Chem. Commun., 1997, 1701 RSC.
  11. B. Nordén, P. Lincoln, B. Åkerman and E. Tuite, in Metal Ions in Biological Systems, eds. A. Siegel and H. Siegel, Marcel Dekker, New York, 1996, vol. 33, pp. 177–252 Search PubMed.
  12. A. H. Elcock and J. A. McCammon, J. Am. Chem. Soc., 1995, 117, 10 161 CrossRef CAS.
  13. A. Pullman and B. Pullman, Q. Rev. Biophys., 1981, 14, 289 CrossRef CAS.
  14. A. M. J. Fichtinger-Shepman, J. L. van der Veer, J. H. J. den Hartog, P. H. M. Lohman and J. Reedijk, Biochemistry, 1985, 24, 707 CrossRef CAS.
  15. J. Reedijk, Chem. Commun., 1996, 801 RSC.
  16. K. J. Yarema, J. M. Wilson, S. J. Lippard and J. M. Essigmann, J. Mol. Biol., 1994, 236, 1034 CrossRef CAS.
  17. M. N. Lipsett, J. Biol. Chem., 1965, 240, 3975 CAS.
  18. W. T. Melvin, H. B. Milne, A. A. Slater, H. J. Allen and M. M. Keir, Eur, J. Biochem., 1978, 92, 373 CrossRef CAS.
  19. S. R. Baindur and K. T. Douglas, Biochim. Biophys. Acta, 1987, 923, 66 CrossRef CAS.
  20. H. I. Heitner, S. J. Lippard and H. R. Sunshine, J. Am. Chem. Soc., 1972, 94, 8936 CrossRef CAS.
  21. L. H. Skibsted, Adv. Inorg. Bioinorg. Mech., 1986, 4, 137 Search PubMed.
  22. N. Igarashi-Yamamoto, A. Tajiri, M. Hatano, S. Shibuya and T. Ueda, Biochim. Biophys. Acta, 1981, 656, 1 CrossRef CAS.
  23. S. J. Milder, P. S. Weiss and D. S. Kliger, Biochemistry, 1989, 28, 2258 CrossRef CAS.
  24. Handbook of Chemistry and Physics, ed. D. R. Lide, CRC, Boca Raton, FL, 75th edn., 1995, p. D-102 Search PubMed.
  25. GMELIN, Verlag Chemie, Berlin, 8th edn., 1954, p. 745.
  26. O. Mønsted and L. H. Skibsted, Acta Chem. Scand., Ser. A, 1984, 38, 23.
  27. L. H. Skibsted and J. Bjerrum, Acta Chem. Scand., Ser. A, 1974, 28, 740.
  28. B. S. Maritz and R. van Eldik, J. Inorg. Nucl. Chem., 1976, 38, 1749 CrossRef CAS.
  29. R. S. Coleman and J. M. Siedlecki, J. Am. Chem. Soc., 1992, 114, 9229 CrossRef CAS.
  30. R. S. Coleman and E. A. Kesicki, J. Am. Chem. Soc., 1994, 116, 11 636 CrossRef CAS.
  31. Applied Photophysics Bio-sequential SX-17MV Software Manual, Applied Photophysics, Leatherhead, 1994 Search PubMed.
  32. P. Bugnon, G. Laurenczy, Y. Ducommun, P.-Y. Sauvageat, A. Merbach, R. Ith, R. Tschanz, M. Doludda, R. Bergbauer and E. Grell, Anal. Chem., 1996, 68, 3045 CrossRef CAS.
  33. OLIS 4300S Spectroscopy User's Manual, OLIS, Jefferson, GA, 1988 Search PubMed.
  34. W. R. Mason, Inorg. Chem., 1970, 9, 2688 CrossRef CAS.
  35. J. Ventegodt, B. Øby and L. H. Skibsted, Acta Chem. Scand., Ser. A, 1985, 39, 453.
  36. S. Elmroth, L. H. Skibsted and L. I. Elding, Inorg. Chem., 1989, 28, 2703 CrossRef CAS.
  37. S. K. C. Elmroth and L. I. Elding, Inorg. Chem., 1996, 35, 2337 CrossRef CAS.
  38. A. Ericson, L. I. Elding and S. K. C. Elmroth, J. Chem. Soc., Dalton Trans., 1997, 1159 RSC.
  39. L. I. Elding and A.-B. Gröning, Acta Chem. Scand., Ser. A, 1978, 32, 867.
  40. P. v. Z. Bekker and W. Robb, Inorg. Nucl. Chem. Lett., 1972, 8, 849 Search PubMed.
  41. L. Carlsson and G. Lundgren, Acta Chem. Scand., 1967, 21, 819 CAS.
  42. A. R. Curtis and W. P. Sweetenham, in FACSIMILE/CHEKMAT User's Manual, Harwell Laboratory, 1988 Search PubMed.
  43. W. J. Louw and W. Robb, Inorg. Chim. Acta, 1974, 9, 33 CrossRef CAS.
  44. A. Psoda, Z. Kazimierczuk and D. Shugar, J. Am. Chem. Soc., 1974, 96, 6832 CrossRef CAS.
  45. J. Leszczynski, J. Phys. Chem., 1993, 97, 3520 CrossRef CAS.
  46. T. Shi, J. Berglund and L. I. Elding, Inorg. Chem., 1996, 35, 3498 CrossRef CAS.
  47. R. Jacobs, F. Prinsloo and E. Breet, J. Chem. Soc., Chem. Commun., 1992, 212 RSC.
  48. C. I. Sanders and D. S. Martin, jun., J. Am. Chem. Soc., 1961, 83, 807 CrossRef.
  49. L. Cattalini, A. Orio and M. L. Tobe, J. Am. Chem. Soc., 1967, 89, 3130 CrossRef CAS.
  50. K. Kaas and L. H. Skibsted, Acta Chem. Scand., Ser. A, 1985, 39, 1.
  51. A. Ericson, J. McCary, R. S. Coleman and S. K. C. Elmroth, unpublished work.
Click here to see how this site uses Cookies. View our privacy policy here.