Advertisement

Analytical Applications of Vibrational Spectroscopy in Bioorganometallic Chemistry

  • Ian S. Butler
Chapter
Part of the NATO ASI Series book series (ASEN2, volume 26)

Abstract

An organometallic compound strictly contains at least one metal-carbon bond, but nowadays, compounds containing an organic moiety linked to a metal through oxygen, sulfur, nitrogen, phosphorus, etc., are also usually considered as organometallics or metal-organics. It is about 45 years since the famous discovery of ferrocene, Cp2Fe (Cp = η5-C5H5), and the birth of organometallic chemistry. In the interim, organometallic chemistry has become a mature field with several major journals being devoted solely to it:, among them, Organometallics, Journal of Organometallic Chemistry and Applied Organometallic Chemistry. Recently, there has been a growing interest in the interactions of organometallic compounds with biomolecules and the new field of bioorganometallic chemistry has opened up [1]. Among the earliest known examples of bioorganometallic compounds are the metallocene dihalides, (Cp2MX2; M = Ti, Zr, Hf, Mo, V; X = Cl, Br), which are active antitumor agents that are presumed to coordinate to DNA in a manner similar to, cis-Pt(NH3)2Cl2 (cis-platin), in which the two halides are displaced from the coordination sphere of the metal by the N atoms of two nearby amino acids. Several areas in which bioorganometallic chemistry plays an important role will now be described, with particular emphasis on the role of vibrational spectroscopy in this work.

Keywords

Surface Enhance Raman Scattering Organometallic Chemistry Organometallic Compound Vibrational Spectroscopy Metal Carbonyl 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    (a) Jaouen, G., Vessieres, A. and Butler, I.S. (1093) Bioorganometallic chemistry — a future direction for transition metal organometallic chemistry, Acc. Chem. Res., 26, 361–366; (b) Butler, I.S. Vessieres, A. and Jaouen, G. (1989) Application of organotransition metal carbonyl complexes as infrared markers for hormonal steroids in biological processes. Comments Inorg. Chem. 8, 269-286.CrossRefGoogle Scholar
  2. 2.
    (a) Butler, I.S. (1977) Transition-metal thiocarbonyl and selenocarbonyls. Acc. Chem. Res. 10, 359–365: (b) Butler, I.S. (1988) (Coordination chemistry of the thiocarbonyl ligand, Pure and Appl. Chem. 60, 1741-1745.CrossRefGoogle Scholar
  3. 3.
    Pouskouleli, G. Butler, I.S. and Hickey, J.P. (1980) Reactions of group VIB metal hexacarbonyls with hormonal steroids, J. Inorg. Nucl. Chem. 42, 1659–1667.CrossRefGoogle Scholar
  4. 4.
    (a) Vessieres, A., Top, S., Ismail, A.A., Butler, I.S., Louer, M. and Jaouen, G. (1988) Organometallic estrogens. Synthesis, interaction with lamb uterine estrogen receptor, and detection by infrared speetroscopy. Biochemistry, 27, 6659–6666; (b) Salmain, M. Vessieres, A., Butler, I.S. and Jaouen, G. (1991) FT-ir spectroscopic method for the trace analysis of metal carbonyl-labeled bioligands. Anal. Chem. 63 CrossRefGoogle Scholar
  5. 5.
    Abel, E.W. and Butler, I.S. (1967) Intensity of earbonyl stretching modes in certain halogenocarbonyl derivatives of chromium, molybdenum, tungsten, manganese, rhenium and iron, Trans. Faraday Soc. 63, 45–55.CrossRefGoogle Scholar
  6. 6.
    (a) Jaouen, G. Vessieres, A. Top, S., Ismail, A.A. and Butler, I.S. (1984) Voie d’ application inédite des complexes des metaux carbonyles. Exemple dans la détection du récepteur de I’ œstradiol, Comp., Rend. Acad. Sc. Paris Ser. II, 298, 683–686; (b) Jaouen, G., Vessieres, A., Top, S., Ismail, A.A. and Butler, I.S. (1985) Metal carbonyls fragments as a new class of markers in molecular biology, J. Amer. Chem. Soc. 107, 4788-4780.Google Scholar
  7. 7.
    Ismail, A.A. (1985) Chalcocarbonyl chemistry: applications in hormone receptor determination, metallo-porphyrins and metal-arene bond activation. Ph.D. Thesis, McGill University, Montreal, Quebec, Canada.Google Scholar
  8. 8.
    Vessieres, A., Jaouen, G., Salmain, M. and Butler, I.S. (1990) An ultra-low volume, gold light-pipe cell for the ir analysis of dilute organic solutions, Appl. Spectrosc., 44, 1097–1094.CrossRefGoogle Scholar
  9. 9.
    Jaouen, G., Vessieres, A., Top, S., Savignac, M., Ismail, A.A. and Butler, I.S. (1987) Transition-metal carbonyl clusters as novel infrared markers for estradiol receptor site detection. Organometallics, 6, 1985–1987.CrossRefGoogle Scholar
  10. 10.
    Salmain, M., Vessieres, A., Brossier, P., Butler, I.S. and Jaouen, G. (1992) Carbonylmetalloimmunoassay (CMIA), a new type of non-radioisotropic immunoassay. I. Principles and application ot phenobarbital assay, J. Immunol. Methods, 148, 65–75.CrossRefGoogle Scholar
  11. 11.
    Philomin, V., Vessieres, A. and Jaouen, G. (1994) New applications of carbonylmetalloimmunoassay (CMIA); A non-radioisotopic approach to cortisol assay, J. Immunol. Methods, 111, 201–210.CrossRefGoogle Scholar
  12. 12.
    Varenne, A., Vessieres, A. and Jaouen, G., unpublished results.Google Scholar
  13. 13.
    Rohr, T.E., Cotton, T.M., Ni, F. and Tarcha, P.J. (1989) Immunoassay employing surface-enhanced Raman spectroscopy, Anal. Biochem. 182, 388–398.CrossRefGoogle Scholar
  14. 14.
    Barnett, S.M., Vlckova, B., Butler, I.S. and Kanigan, T.S. (1994) Surface enhanced Raman scattering (SERS) spectroscopic study of 17α-ethinylestradiol on silver colloid and in glass-deposited Ag-17α-ethinylestradiol, Anal. Chem. 66, 1762–1765.CrossRefGoogle Scholar
  15. 15.
    Feilcheneld, H. and Weaver, M.J. (1989) Binding of alkynes to silver, gold and underpotential-deposited silver electrodes as deduced by surface-enhanced Raman spectroscopy, J. Phys. Chem., 93, 4276–4282.CrossRefGoogle Scholar
  16. 16.
    Salmain, M., Vessieres, A., Top, S., Jaouen, G. and Butler, I.S. (1985) Analytical potential of near-infrared Fourier transform Raman spectroscopy in the detection of solid transition metal carbouyl steroid hormones, J. Raman Spectrosc., 26, 31–38.CrossRefGoogle Scholar
  17. 17.
    Barnett, S.M., Butler, J.S., Top, S. and Jaouen, G. (1995) Pressure-tuning infrared and solution Raman spectroscopic studies of 17β-estradiol and some A-ring and 17α-ethinylestradiol derivatives, Vibrational Spectrosc., 8, 263–277.CrossRefGoogle Scholar
  18. 18.
    Markwell, R.M. and Butler, I.S. (1966) On the use of diamond as a pressiure calibraut for near-infrared FT-Raman microspectroscopy at high pressures, Can. J. Chcm., 73, 355–359.Google Scholar

Copyright information

© Springer Science+Business Media Dordrecht 1997

Authors and Affiliations

  • Ian S. Butler
    • 1
  1. 1.Department of ChemistryMcGill UniversityMontrealCanada

Personalised recommendations