Synthesis and structure characterization of selenium metabolites†

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Teresa W.-M. Fan, Andrew N. Lane, Dean Martens and Richard M. Higashi


Abstract

The difficulty in determining trace-level organoseleno metabolites and the lack of commercially available standards have been major barriers to a molecular-level understanding of Se biogeochemistry, ecotoxicology and nutrition, particularly in aquatic ecosystems. To overcome the problem, three important precursors of volatile alkyl selenides were synthesized, including dimethylselenonium propionate (DMSeP), which has only been postulated to exist in nature. A combination of 2-D multinuclear NMR, electrospray MS and GC–MS methods was employed to identify DMSeP, methylselenomethionine and methylselenocysteine in synthetic preparations without extensive clean-up. An alkaline hydroelimination test coupled with GC–MS analysis for the release pattern of dimethyl selenide (DMSe) and dimethyl diselenide (DMDSe) was developed for a diagnostic determination of the three products. The DMSe release pattern of DMSeP confirmed the presence of a DMSeP-like compound in the biomass of 100 mg l–1 Se-treated Chlorella investigated previously. Silylation–GC–MS was tested for the determination of selenomethionine, selenocysteine and methylselenocysteine in a standard mixture with a detection limit of better than 1 pmol per 0.5 µl injection volume for selenomethionine. This method was applied to the analysis of the acid digest of the proteinaceous fraction of the Chlorella culture. Selenomethionine was found to contain >70% of the protein-bound Se, although this constituted only a minor fraction of the total Se in the Chlorella biomass. These findings revealed the metabolic relationship between Se volatilization and selenomethionine incorporation into proteins. This knowledge is critical to advancement in Se biogeochemistry, ecotoxicology and the development of in situ bioremediation schemes.


References

  1. H. E. Ganther, In Selenium, ed. Zingaro, R. A., and Cooper, W. C., Van Nostrand Reinhold, New York, 1974, pp. 546–614 Search PubMed.
  2. K. Swarz and C. M. Foltz, J. Am. Chem. Soc., 1957, 79, 3292 CrossRef CAS.
  3. K. J. Maier and A. W. Knight, Rev. Environ. Contam. Toxicol., 1994, 134, 31 Search PubMed.
  4. T. W.-M. Fan and R. M. Higashi, in Environmental Chemistry of Selenium, ed. Frankenberger, W. T., Jr., and Engberg, R. A., Marcel Dekker, New York, 1998, pp. 545–563 Search PubMed.
  5. F. Shimazu and A. L. Tappel, Science, 1964, 143, 369 CAS.
  6. S. N. Nigam and W. B. McConnell, Biochim. Biophys. Acta, 1969, 192, 185 CrossRef CAS.
  7. J. J. Wrench, Mar. Biol., 1978, 49, 231 CrossRef CAS.
  8. N. R. Bottino, C. H. Banks, K. J. Irgolic, P. Micks, A. E. Wheeler and R. A. Zingaro, Phytochemistry, 1984, 23, 2445 CrossRef CAS.
  9. H. E. Ganther, R. J. Kraus and S. J. Foster, Methods Enzymol., 1984, 107, 582 CrossRef.
  10. T. Oikawa, N. Esaki, H. Tanaka and K. Soda, Proc. Natl. Acad. Sci. USA, 1991, 88, 3057 CAS.
  11. M. Politino, L. Tsai, Z. Veres and T. C. Stadtman, Proc. Natl. Acad. Sci. USA, 1990, 87, 6345 CAS.
  12. W. C. Hawkes and M. A. Kutnink, J. Chromatogr., 1992, 576, 263 CrossRef CAS.
  13. B. Neuhierl and A. Böck, Eur. J. Biochem., 1996, 239, 235 CrossRef CAS.
  14. T. D. Cooke and K. W. Bruland, Environ. Sci. Technol., 1987, 21, 1214.
  15. T. W.-M. Fan, A. N. Lane and R. M. Higashi, Environ. Sci. Technol., 1997, 31, 569 CrossRef CAS.
  16. R. S. Oremland, in Selenium in the Environment, ed. Frankenberger, W. T., Jr., and Benson, S., Marcel Dekker, New York, 1994, pp. 389-419 Search PubMed.
  17. F. Challenger and M. I. Simpson, J. Chem. Soc., 1948, 3, 1591 RSC.
  18. G. Toennies and J. J. Kolb, J. Am. Chem. Soc., 1945, 67, 849 CrossRef CAS.
  19. S. J. Foster and H. E. Ganther, Anal. Biochem., 1984, 137, 205 CrossRef CAS.
  20. R. H. White, J. Mar. Res., 1982, 40, 529 Search PubMed.
  21. T. W.-M. Fan, R. M. Higashi, A. N. Lane and O. Jardetzky, Biochim. Biophys. Acta, 1986, 882, 154 CrossRef CAS.
  22. T. W.-M. Fan, R. M. Higashi, T. A. Frenkiel and A. N. Lane, J. Exp. Bot., 1997, 48, 1655 Search PubMed.
  23. D. Martens, unpublished work.
  24. V. Sklenár, H. Higashiro, G. Zon, H. T. Miles and A. Bax, FEBS Lett., 1986, 208, 94 CrossRef.
  25. M. Rance, O. W. Sørensen, G. Bodenhausen, G. Wagner, R. R. Ernst and K. Wüthrich, Biochem. Biophys. Res. Commun., 1983, 117, 479 CrossRef CAS.
  26. T. W.-M. Fan, Prog. Nucl. Magn. Reson. Spectrosc., 1996, 28, 161 CrossRef CAS.
  27. A. Bax and D. Marion, J. Magn. Reson., 1988, 78, 186 CAS.
  28. H. Duddeck, Prog. Nucl. Magn. Reson. Spectrosc., 1994, 27, 1 CrossRef CAS.
  29. T. W.-M. Fan and A. N. Lane, unpublished work.
  30. B.-A. G. Lewis, in Environmental Biogeochemistry. Carbon, Nitrogen, Phosphorus, Sulfur and Selenium Cycles, ed. Nriagu, J. O., Ann Arbor Science Publishers, Ann Arbor, MI, 1976, vol. 1, pp. 389–409 Search PubMed.
  31. R. E. Huber and R. S. Criddle, Arch. Biochem. Biophys., 1967, 122, 164 CrossRef CAS.
  32. J. W. Doran, Adv. Microb. Ecol., 1982, 6, 1 Search PubMed.
  33. J. F. Hudman and A. R. Glenn, Arch. Microbiol., 1984, 140, 252 CrossRef CAS.
  34. R. S. Oremland, J. T. Hollibaugh, A. S. Maest, T. S. Presser, L. G. Miller and C. W. Culbertson, Appl. Environ. Microbiol., 1989, 55, 2333 CAS.
  35. T. W.-M. Fan and R. M. Higashi, unpublished work.
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